JPS5851003B2 - Polyolefin manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins using a supported catalyst capable of producing olefin polymers in high yields over a long period of time.

More specifically, the present invention relates to an olefin polymerization method capable of producing a highly stereoregular polymer of α-olefin having 3 or more carbon atoms in high yield.

Conventionally, a combination system of a solid titanium halide and an organoaluminum compound has been widely used as a catalyst for producing highly stereoregular polymers of α-olefins.

Polymerization using this catalyst system yields polymers with high stereoregularity, but the yield of polymer per titanium catalyst remains at a low level. It takes.

A method of synthesizing a titanium catalyst by reacting a titanium halogen compound with various powdered solid substances, and then combining this with an organometallic compound to perform highly active polymerization of olefins, in order to increase the polymer yield per titanium catalyst. have been proposed many times.

In the highly active polymerization of α-olefins having 3 or more carbon atoms, from industrial knowledge, it goes without saying that the polymer yield per unit catalyst or per titanium and the stereoregularity index of the produced polymer are important. However, the particle size distribution of the produced polymer also has an important meaning.

For example, if there are many particulate polymers, it is difficult to completely separate the polymer from the polymer slurry and the polymerization solvent, resulting in a disadvantage in terms of yield.

Therefore, in the present invention, when applied to the polymerization of α-olefins having 3 or more carbon atoms, a supported catalyst component is capable of producing a small particulate polymer and obtaining a highly stereoregular polymer in high yield. The object of the present invention is to provide a method for polymerizing olefins using the same.

That is, the present invention provides a titanium-containing solid catalyst component (a) derived from an interaction product of an organomagnesium compound and a polysiloxane, an organic acid ester, and a titanium compound, and an organometallic compound of a metal from Group 1 to Group 3 of the periodic table. (b
) is a method for producing polyolefins, characterized by polymerizing or copolymerizing olefins in the presence of a catalyst.

Each raw material component used in the present invention will be explained below.

Organomagnesium compounds are compounds having magnesium directly bonded to at least one carbon atom.

These can be represented, for example, by the general formula R/MgR//, where R' represents an alkyl group, cycloalkyl group, or aryl group, R" represents a halogen or the same organic group as R', and R" represents R' may be the same as

The above organomagnesium compound is commonly called a Grignard reagent, and is generally used in the form of an adduct with an ether such as tetrahydrofuran.

In the present invention, it is also possible to use the compound in the form of an ether adduct, but a compound that is not in the form of an ether adduct may also be used.

For example, Journal of the Chemical Society, 1
961, p. 1175, i.e., a Grignard reagent synthesized in a solution in a common inert solvent.

Specific examples of the compounds are shown below.

CH3MgCl, CH3MgBr, CH3MgI:
C2H6MgCL C2H5MgBr, C2H5MgI
:C3H7MgCl, C3H7MgBr, C3H7M
gI: C4H9MgCl, C4HgMgBr1C4H
gMgI: C5H, □MgC1, C5H11MgBr
, C5H11MgI :C6H,3MgC11C6H1
3MgBr1C6H13MgI:C7H, 5MgBr,
C7H15MgI; C3H1□MgCl.

C3Hl 1MgB r , C8n, □Mg I:
Cg HlgMgCI, C9H, gMgBr, CgH
lgMgI; C10HC10H20; C6H5MgC
l, C6H5MgBr, C6H5MgI :CH3(C
a H4) MgC1, CH3(C6H4)MgBr.

Halogen-containing organomagnesium compounds such as CHa (Ca H4) Mg I;
H3) 2, Mg(C2Hs)2, Mg(C3Hz)2
, Mg (C4H9) 2, Mg(CsHt□) 2
, Mg (Ca Ht 3)2, Mg (C7H15)
2, Mg(CH3)(C2H5), Mg(C2H5)(
C3H7), Mg (CH3) (C4H9), Mg(
C2H5)(C4H9), Mg(CaH5)2, Mg
l: CH3(C6H4)J2, Mg(C2H5)(C6
H5), Mg(C,, H5)(CH3(C6H4)J, and other dialkylmagnesium compounds.

Further, the organomagnesium compound includes AI.

It may contain metals other than Mg such as Zn and B, and these compounds can be synthesized using a similar method as shown in Journal of Organometallic Chemistry, Vol. 93, p. 1, 1975. be able to.

Examples of polysiloxanes include the following.

(1) A linear polysiloxane represented by the general formula Q(Q2SiO)n5iQ3 (where Q is hydrogen, a hydroxyl group, an alkyl group containing usually 1 to 4 carbon atoms, a cycloalkyl group containing usually 3 to 8 carbon atoms) , carbon atoms usually 6
aryl group containing from 1 to 8 carbon atoms and from 1 to 1 carbon atoms
An alkoxy group or a phenoxy group containing two groups, which may be the same or different.

However, this excludes cases where all Q are hydrogen and hydroxyl groups.

n usually represents an integer from 1 to 1000).

Such linear polysiloxanes include, for example, hexamethyldisiloxane, decamethyltetrasiloxane, tetracosamethylundecasiloxane, 3-hydroheptamethyltrisiloxane, 3,5-dihydrooctamethyltetrasiloxane, 3,5,7 - Dolihydrononamethylpentasiloxane, tetramethyl-1,3-diphenyldisiloxane, pentamethylto-3,5-triphenyltrisiloxane, heptaphenyldisiloxane, octaphenyltrisiloxane, methylfolysiloxane, phenylmethylpolysiloxane be.

(11) Cyclic (cyclo)polysiloxane represented by the general formula (Q2' S tO) p (where Q' is hydrogen, an alkyl group usually containing 1 to 4 carbon atoms, and usually containing 3 to 8 carbon atoms) a cycloalkyl group, an aryl group containing usually 6 to 8 carbon atoms, and an alkoxy group containing usually 1 to 12 carbon atoms, a phenoxy group,
They may be the same or different.

However, p usually represents an integer from 1 to 1ooo, except when all Q' are hydrogen).

Examples of such cyclopolysiloxanes are 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octantylcyclotetrasiloxane, decamethylcyclopenda These are siloxane, dodecamethylcyclohexasiloxane, triphenyl-1,3,5-trimethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, and octantylcyclotetrasiloxane.

Of course, if Q or Q' in the above formula is an organic group,
It may have a substituent such as a halogen or a hydroxyl group.

Examples of the organic acid ester used for preparing the titanium-containing solid catalyst component include the following.

(1) Fatty acid ester, (11) alicyclic ester and (m) aromatic ester.

(1) Those commonly used as aliphatic esters include saturated or unsaturated fatty acid carboxylic acids containing usually 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, or their halogen-substituted products, and usually 1 to 18 carbon atoms. , preferably 1 to 4 saturated or unsaturated aliphatic alcohols, usually 3 to 8 carbon atoms, preferably 5
and saturated or unsaturated aliphatic alcohols containing 6 or phenols containing usually 6 to 10, preferably 6 to 8 carbon atoms or carbon bonded to alicyclic or aromatic rings containing usually 3 to 10 carbon atoms. These include esters, lactones, carbonic esters, etc. with aliphatic saturated or saturated alcohols containing usually 1 to 4 atoms.

(11) Those commonly used as alicyclic esters include alicyclic carboxylic acids having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated carbon atoms having usually 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Alternatively, it is an ester of an unsaturated aliphatic alcohol.

(iii) Those commonly used as aromatic esters include, for example, aromatic carboxylic acids containing usually 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and aromatic carboxylic acids containing usually 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms. saturated or unsaturated aliphatic alcohols containing, phenols containing usually 3 to 8, preferably 6 to 8 carbon atoms, or carbon bonded to alicyclic or aromatic rings containing usually 3 to 10 carbon atoms. They are esters or aromatic lactones with fatty saturated or unsaturated alcohols containing usually 1 to 4 atoms.

These esters will be specifically explained below.

The above (1) aliphatic ester is illustrated below.

Methyl formate, ethyl acetate, n-amyl acetate, 2-acetic acid
- Saturated fatty acids such as ethylhexyl, n-butyl formate, ethyl butyrate, ethyl valerate - grade alkyl, vinyl acetate,
Saturated aliphatic alkenyls such as allyl acetate, unsaturated fatty acid-class alkyls such as methyl acrylate, methyl methacrylate, and n-butyl crotonate.

Haloaliphatic monocarboxylic acid esters such as methyl chlorate and ethyl dichloroacetate.

Lactones such as propiolactone, γ-butyrolactone, and δ-valerolactone, and carbonic acid esters such as ethylene carbonate.

The above-mentioned (II) alicyclic ester is illustrated below.

Methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecarboxylate, ethyl methylcyclohexanecarboxylate.

Said O! i) %” aromatic esters are illustrated below.

Alkyl benzoate (where the alkyl group is a saturated or unsaturated hydrocarbon radical containing usually from 8 to 8 carbon atoms, preferably from 1 to 4 carbon atoms), such as ethyl benzoate, ethyl benzoate, n-benzoate and i-propyl,
n-11-5ec- and tert-butyl benzoate, n- and i-amyl benzoate, n-hexyl benzoate, n-octyl and 2-ethylhexyl benzoate, vinyl benzoate, aldyl benzoate, preferably benzoic acid Methyl and ethyl, cycloalkyl benzoates (where the cycloalkyl group is a non-aromatic cyclic hydrocarbon radical containing usually 3 to 8 carbon atoms, preferably 5 and 6 carbon atoms), such as cyclopentyl benzoate, cyclohexyl benzoate , aryl benzoate (where the aryl group is usually 6 carbon atoms)
hydrocarbon groups containing from 1 to 10, preferably from 6 to 8, to the ring to which halogen and/or alkyl groups, usually 1 to 4 carbon atoms, may be attached), such as phenyl benzoate, -4-benzoate; Tolyl, benzyl benzoate, styryl benzoate, 2-chlorophenyl benzoate,
4-chlorobenzyl benzoate, aromatic monocarboxylic acid ester with an electron-donating substituent, such as a hydroxy group, alkoxy group, or alkyl group attached to the aromatic ring, oxybenzoic acid ester (herein, the alkyl group of the ester, cycloalkyl group and aryl group are the same as above),
For example, methyl salicylate, ethyl salicylate, 1-butyl salicylate, 1-amyl salicylate, aldyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, n-propyl p-oxybenzoate, p
-5ec-butyl oxybenzoate, 2-ethylhexyl p-oxybenzoate, cyclohexyl p-oxybenzoate, phenyl salicylate, 2-tolyl salicylate, benzyl salicylate, phenyl p-oxybenzoate,
3-Tolyl p-oxybenzoate, Hensyl p-oxybenzoate, ethyl α-resorcinate, alkoxybenzoic acid ester (here, the alkyl group constituting the alkoxy group is usually an alkyl group containing 1 to 4 carbon atoms) , preferably a methyl group and an ethyl group, the alkyl group and aryl group of the ester are the same as above), such as methyl anisate, ethyl anisate, anisate-1
-propyl, 1-7” thyl anisate, phenyl anisate, benzyl anisate, ethyl 0-methoxybenzoate,
Methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, n-7” thyl p-ethoxybenzoate, ester p-alkoxybenzoate, phenyl p-ethoxybenzoate, methyl 0-ethoxybenzoate, ethyl peratorumate , asym-ethyl guaiacolcarboxylate, alkyl benzoate ester (wherein the alkyl group bonded to the aromatic ring of benzoic acid is a saturated or unsaturated hydrocarbon group usually containing 1 to 8 carbon atoms, and the alkyl group of the ester and (Aryl groups are the same as above), such as methyl p-toluate, ethyl p-toluate, -i-7'lopyl p-)toluate, -n- and -1-toluate.
Amyl, aldyl p-toluate, phenyl p-toluate, 2-)dyl p-)toluate, ethyl 0-toluate, ethyl m-toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate , p-ethylbenzoic acid-
8ee-butyl, mepropyl 0-ethylbenzoate, m
-n-7'' ethylbenzoate, ethyl 3-5-xylenecarboxylate, ethyl p-styrenecarboxylate.

Amino group-containing benzoic acid esters, such as methyl p-aminobenzoate, ethyl p-aminobenzoate.

Naphthoate esters, such as methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate.

Aromatic lactones, such as coumarins, phthalides.

Preferred among these are esters of benzoic acid, alkylbenzoic acids, alkoxybenzoic acids, especially alkyl esters containing 1 to 4 carbon atoms of benzoic acid, 0- or p-)ruyl acid or p-anisic acid. Esters, especially methyl or ethyl esters are preferred.

There are various titanium compounds used in the production reaction of the solid catalyst component, but they are usually tetravalent titanium compounds represented by the formula Ti(OR)X4-g (R is an alkyl group, X is a halogen, O≦g≦4). Titanium compounds are preferred.

More specifically, titanium tetrahalides such as TiCl4, TiBr4, TiI4; Ti(OCH3)C13
, Ti(OC2H5)C13, Ti(On C4H9)
C13, Ti(OC2H3)Br3, Ti(OisoC
4H9) Turinated alkoxytitanium such as Br3; Ti(OCH3)2C12, Ti(OC2H5)2
CI2, T I (On c4Ho) 2 Cl,
Dihalogenated alkoxy titanium such as T I (OC2H5) 2Br 2; Ti(OCH3)3CL Ti(OC2H5)3C1,
Ti(On-C4Hg)3C1,,Ti(OC2H5)
Monochlorogenated trialkoxytitanium such as 3Br;
T i (OCH3) 4, Ti (OC2H5) 4, T
Tetraalkoxytitanium such as i(On-C4Hg)4 can be exemplified.

Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

There are various methods for producing the titanium-containing solid catalyst component (a), including a method in which a mutual reaction product of the organomagnesium compound and polysiloxane is brought into contact with an organic acid ester, and then reacted with a titanium compound. It is preferable to take

Various known methods can be used to react the organomagnesium compound and polysiloxane, and the reaction can be carried out in ether or an inert solvent solution.

In addition to using an organomagnesium compound once synthesized, we can also use metallic magnesium and polysiloxane together,
The above-mentioned mutual reactants may be synthesized while an organomagnesium compound is synthesized by adding an alkyl halide or the like.

The reaction temperature is from room temperature to 300°C, in which case the reaction time is preferably from about 30 minutes to about 10 hours.

The molar ratio of the organomagnesium compound to the polysiloxane varies depending on the type of each compound used, but it is 0.1 to 1 silicon atom per 1 atom of magnesium.
It is preferable to set it to 0 atoms.

In the above reaction, if the reaction product does not precipitate as a solid, the reaction product can be obtained by removing the light fraction during the reaction or from the reaction wave, and the solvent by distillation.

Although the details of these mutual reactants are still unclear, measurements of infrared absorption spectra revealed that S of polysiloxane
The absorption band of the i -0-S i bond disappears, and the 800
A new absorption band appears between ~1000 cIIL-1.

This indicates that the organomagnesium compound reacted with the polysiloxane, and the reason for the appearance of this new absorption band is thought to be due to the formation of Si-0-Mg bonds in the reactant. .

The preferred mutual reactant is Mg/Si (molar ratio)
is 0.1 to 10, and Mg-carbon bonds have substantially disappeared.

These mutual reactants may also contain other magnesium compounds.

For example, a small amount of a reaction product of an organomagnesium compound and an electron donor or a magnesium halide may be contained.

A co-pulverization method can be cited as a method for bringing the mutual reactant and the organic acid ester into contact.

Various methods can be used for the addition order and addition method in the co-pulverization process.

During grinding, inorganic or organic fillers, such as LiC
1, CaCO3, CaCl2.5rC1□, BaC12
, Na2SO4, Na2CO3, TiO2, NaB4O
7, Ca3 (PO3) 2, CaSO4, B a C
Os, Al2(SO4)3, B2O3, Al2O3,5
i02, polyethylene, polypropylene, polystyrene, etc. may also coexist.

The co-pulverization process is carried out in the substantial absence of oxygen, water, etc. using, for example, a ball mill, vibration mill, impact mill, or the like.

The charging ratio of the mutual reactant and the organic acid ester in co-pulverization is preferably about 0.001 to about 10 times the mole of the former, more preferably about 0.01 to about 5 moles, particularly preferably about 5 moles of the latter per 1 atom of magnesium. is about 0.01
from about 1 mole.

It is preferable to select the grinding conditions appropriately depending on the type of raw material and the grinding equipment, but in general, the grinding time is 1 hour to 10 days, and the grinding temperature should be selected around room temperature (
, there is no need for particular cooling or heating.

For example, a vibration mill is made of stainless steel (SUS 32
) Ceramic production capacity 800TL! ! , 2.8 kg of stainless steel (SUS 32) balls with a diameter of 15 mm are housed in a ball mill cylinder with an inner diameter of 100 mm, and 20 to 40 of the objects to be processed are
When S' is charged, it is preferable to carry out the crushing process at an impact acceleration of 7 G for 6 hours or more, preferably for 24 hours or more.

When reacting a titanium compound in the method for producing the titanium-containing solid catalyst component (a), there is usually a method in which the titanium compound is allowed to coexist during the above-mentioned pulverization, or a method in which the product of such a method is further reacted with a titanium compound in the liquid phase or gas phase. , a method of reacting the pulverized material with a titanium compound, etc. can be adopted.

When co-pulverizing a titanium compound, it can also be used in the form of a complex compound with an organic acid ester.

When a titanium compound is also co-pulverized, the amount of titanium compound used is preferably about 0.00% titanium per 1 atom of magnesium.
0.001 to about 10 atoms, more preferably about 0.01 to about 1 atom.

Although this pulverized product may be used as it is as the solid catalyst component (a) with or without washing, it is preferable to use a catalyst obtained by reacting a liquid phase titanium compound in the final stage of catalyst preparation.

In order to make a titanium compound act in a liquid phase, a liquid titanium compound such as titanium tetrachloride can be added alone or dissolved in an inert solvent such as hexane, heptane, or kerosene. A method of suspending the pulverized material is preferred.

According to this method, the influence of minute amounts of impurities during the pulverization process is small, and the ratio of the amount of raw materials used can be varied over a wide range.

The titanium compound used in this method varies depending on the amount of the organic acid ester used previously, but
Usually about 0.001 titanium atoms per 1 atom of magnesium
The titanium compound is preferably used in proportions ranging from about 1000 atoms to about 1000 atoms, preferably about 0.05 atoms or more.

There is no particular restriction on the temperature at which the liquid phase titanium compound is applied, but it is usually about 20 to about 200° C. and preferably about 0.5 hours or more.

After the treatment, the solid contact component (a) is preferably isolated by filtration, thoroughly washed with an inert solvent, and then subjected to polymerization.

The contact reaction between the above-mentioned mutual reactants containing magnesium and silicon and the organic acid ester can also be carried out in an inert solvent, for example, a hydrocarbon solvent such as hexane or heptane kerosene.

The amount of the organic acid ester used is preferably about 0.01 to about 1 mole per mole of magnesium in the mutual reactant containing magnesium and silicon.

It is sufficient to carry out the reaction for about 5 minutes to 2 hours at a reaction temperature of room temperature to about 200°C.

After the reaction is completed, the reaction product can be isolated by filtering, evaporating, etc. and washing with an inert solvent.

The reaction between this reactant and the titanium compound can be carried out in accordance with the reaction method for the co-pulverized product and the titanium compound.

Although it varies depending on the catalyst preparation conditions, the typical composition of the solid catalyst (a) preferable as the polymerization catalyst obtained in this way is about 1.0 to 6.0% by weight of titanium, 1% by weight of magnesium,
0.0 to 20.0% by weight, halogen 40 to 70
% by weight, organic acid ester 5.0 to 15.0% by weight,
Their compositions are not substantially changed by washing with hexane at room temperature.

These usually exhibit a surface area of 10 m''/ft or more, preferably 50 m/ft or more.

The organometallic compound of a metal from Group 1 to Group 3 of the periodic table used as the catalyst component (b) is one having a hydrocarbon group directly bonded to the metal, such as an alkyl aluminum compound,
Examples include alkyl aluminum alkoxide, alkyl aluminum hydride, alkyl aluminum halide, alkyl aluminum alkoxide, dialkyl zinc, dialkyl magnesium, and alkyl aluminum halide.

Among these, preferred compounds are AI(C2H5) 3,
Al(CH3)3, AI(C3H7)s, AI(C4H
9) 3, trialkyl or trialkenylaluminum, such as AI (C12H25)s, (C2H5)2
A10Al(C2H5)2, (C4H9)2AIOAl
(C4H9)2, (”2H5)2AINAI(C2H5
) Alkylaluminum compounds with a structure in which many AI atoms are linked together through oxygen or 6H5 nitrogen atoms, such as (C2H5)2AIH1 (C4H9)2AIH, (C2H5)2AICI, (C2H5)2AII .

Dialkyl aluminum halides such as (C4H9)2AICI, (C2H5)2AI(OC2H5), (C2
H5) dialkylaluminum alkoxides or phenoxides such as 2A1(OC6H5), most preferred being trialkylaluminum.

The olefins used for polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc., and these can be subjected to not only homopolymerization but also random copolymerization and block copolymerization.

Further, for copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components.

When used in the polymerization or copolymerization of α-olefins having 3 or more carbon atoms or copolymerization with a secondary amount of ethylene and α-olefins having 3 or more carbon atoms, polymers with high stereoregularity can be obtained in high yields. It will be done.

Polymerization can be carried out in either liquid phase or gas phase.

When carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium.

In the case of liquid phase polymerization, solid catalyst component a) per liquid phase 11
0.001 to 0.5 mmo in terms of titanium atoms
l, and organometallic compounds of metals from Groups 1 to 3 of the periodic table (0.1 to 50 mm when bJ is converted to metal atoms)
It is preferable to keep it at 100 ml.

A molecular weight regulator such as hydrogen may be used during the polymerization.

Furthermore, in order to control stereoregularity of α-olefins having 3 or more carbon atoms, ethers, ethylene glycol derivatives, amines, sulfur-containing compounds, nitriles, esters, carboxylic acids, acid amides, oxyacids, keto acids, Electron donors such as acid anhydrides, acids), rhodanides, and amino acids may also be present (particularly organic acid esters, especially aromatic carboxylic acid esters are preferred).

The type of aromatic carboxylic acid ester is selected from those mentioned above for use in the preparation of the solid catalyst component (a), but particularly preferred are benzoic acid ester and nuclear-substituted benzoic acid ester. esters, toluic acid esters, anilic acid esters, phthalic acid diesters, terephthalic acid diesters, hydroxybenzoic acid esters, aminobenzoic acid esters, and the most preferred ones are p-) methyl tolyate and p-) ethyl tolyate. .

These may be used in the form of addition reaction products with the organometallic compounds.

The effective amount of the compound to be used is usually about 0.001 to about 10 mol, preferably about 0.01 to about 2 mol, particularly preferably about 0.001 to about 10 mol, particularly preferably about 0.01 to about 2 mol, per 1 mol of the organometallic compound.
1 to about 1 mole.

The polymerization temperature of the olefin is preferably about 20 to about 2
00°C, more preferably about 50 to about 180°C,
The pressure is preferably from normal pressure to about 50 kg/crA, preferably about 2 to about 20 kg/crA.

Polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

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

According to the present invention, it is possible to obtain a highly stereoregular polymer in high yield, particularly from an α-olefin having 3 or more carbon atoms.

Example 1 5 omz of commercially available Grignard reagent C2H5MgCI (tetrahydrofuran solution 2 mol/A) was added to 300 ml of refined kerosene.
The bundle silicone TSF-451 (20
centistokes) was further added.

The temperature of the reaction solution was raised to 200° C. while removing light fractions, and when the reaction was allowed to proceed for 30 minutes, a white solid was obtained.

The obtained solid was collected by filtration, washed with hexane, and then dried.

Next, 15g of the above compound and 2rrt13 of ethyl benzoate were added to stainless steel (STJS) with a diameter of 15 mm in a nitrogen atmosphere.
32) Internal volume of 800m containing 100 balls
g, and placed in a stainless steel ball mill cylinder with an internal diameter of 100 mm, and contacted at 125 rpm for ioo hours.

The above solid treated material is titanium tetrachloride 300ml! The suspension was stirred at 80° C. for 2 hours to react.

After the reaction was completed, the solid portion was collected by t-filtration and thoroughly washed with hexane to obtain a titanium-containing solid catalyst component.

The components are 2.5% by weight of titanium, 5.6% by weight of chlorine, 8.5% by weight of magnesium, and 8.2% by weight of ethyl benzoate.
It contained.

Charge 750rni3 of hexane from which oxygen and moisture have been sufficiently removed into an autoclave with an internal volume of 21, and heat triethylaluminum 5,0mm under an atmosphere of propylene at 40°C.
ol and 1.59 mmol of methyl p-toluate were charged, and 5 minutes later, 0.03 mmol of the titanium-containing solid catalyst component was charged in terms of titanium atoms.

The system was heated to 60°C and the total pressure was 7.0 kg/c with propylene.
Pressure increased to rA, followed by 400ml of hydrogen! was introduced and polymerization was carried out for 4 hours.

After the polymerization was completed, the solid component was filtered once, and 1.25% of white powdery polypropylene was obtained. I got it.

The extraction residue with boiling n-hebutane was 95.8%, the bulk specific gravity was 0.38, the melt index was 6.0,
Furthermore, the particle size distribution of the powder was 90% of the particles of 74μ or more.

On the other hand, by concentrating the liquid phase, 8.32% of the solvent-soluble polymer
I got it.

Examples 2 to 5 Catalyst synthesis was carried out in the same manner as in Example 1, except that the bundle silicone TSF 451 in Example 1 was changed to another polysiloxane, and propylene polymerization was carried out.

The results are shown in Table 1.

Example 6 Tork Silicone 5H-6018 was suspended in 202, 100 mA' of hexane.

The system was heated to 60°C, and 23 rul of n-butylmagnesium chloride was added. (Tetrahydrofuran solution 2M/l) at 3
It was added dropwise in 0 minutes, and the mixture was reacted at the same temperature for 1 hour.

After the reaction was completed, the solid portion was collected by filtration at room temperature.

The solid thus obtained was suspended in 300 mA' of kerosene, 3 mg of ethyl benzoate was added, and the mixture was reacted at 80° C. for 1 hour.

The reaction product was collected by E-filtration, washed with hexane, dried, and suspended in 150 mA' of titanium tetrachloride.

The reaction mixture was stirred at 120° C. for 2 hours, and the solid portion was collected by filtration, washed with hexane, and dried to obtain a titanium-containing solid catalyst component.

The components include 5.0% by weight titanium, 56% by weight chlorine, 12% by weight magnesium, and 4.4% by weight ethyl benzoate.

The above titanium-containing solid catalyst component is 0.0 in terms of titanium atom.
When propylene polymerization was carried out in the same manner as in Example 1 except that 3 mmol was used, white powder polypropylene 127y was obtained.

The extraction residue rate with boiling n-hebutane was 95.3%, the bulk specific gravity was 0.36, the melt index was 5.7, and the particle size distribution of the powder was 91% with a particle size of 74μ or more.

On the other hand, a solvent-soluble polymer 7.92 was obtained by concentrating the liquid phase.

Claims (1)

[Scope of Claims] 1. A titanium-containing solid catalyst component (a) derived from an interaction product of an organic magnesium compound and a polysiloxane, an organic acid ester, and a titanium compound, and an organic compound of a group 1 to group 3 metal of the periodic table. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst combined with a metal compound (b). 2. The method according to claim 1, wherein the Mg/Si (molar ratio) in the mutual reactants is from 0.1 to 10. 3. The method according to claim 1, wherein the organic acid ester is an aromatic carboxylic acid ester. 4. The method according to claim 1, wherein the titanium compound is titanium tetrachloride. 5. The method according to claim 1, in which the solid catalyst component (a) is obtained by co-pulverizing the mutual reactant and the organic acid ester and then reacting the same with a titanium compound. 6 As the solid catalyst component (a), about 1.0 to about 6.0% by weight of titanium and about 10.0 to about 20% by weight of magnesium.
．． 0% by weight, about 40.0 to about 70.0% by weight of halogen, and about 5.0 to about 15.0% by weight of organic acid ester. . 7 As the organometallic compound (b), trialkyl 7) L
2. The method according to claim 1, using yminium. 8. The method according to claim 1, characterized in that the polymerization or copolymerization is carried out in the presence of an electron donor, preferably an aromatic carboxylic acid ester, in addition to the solid catalyst acid Ha) and the organometallic compound (b). . 9 Claim 1 in which the olefin is propylene
Method described.