JPH03220207A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst for olefin polymerization having a sharp particle size distribution and a large particle size by combining a titanium halide catalyst component supported by a magnesium compound with an organometallic compound alone or together with an electron donor. CONSTITUTION:A magnesium compound is reacted with a 1-20C (un)saturated mono- or poly-alcohol in the presence of CO2 in an inert hydrocarbon solvent to obtain a component A (step A). Component A is reacted with a titanium halide and/or a vanadyl halide and/or a vanadium halide and/or a halosilane and a siloxane compound to obtain a solid product (I) (step B). The product (I) is reacted with the same alcohol as that used in step A and a cyclic ether, dissolved and reprecipitated to obtain a solid product (II) (step C). The product (II) is reacted with component B comprising the titanium halide and/or the vanadyl halide and/or the vanadium halide which are the same as there used above to obtain a solid product III, which is reacted with a mixture of component B with an electron donor to obtain a catalyst component as a solid product IV (step D). This catalyst component is combined with an organometallic compound alone or together with an electron donor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for alpha olefin polymerization, and in particular to a titanium halide catalyst component supported on a magnesium compound and a catalyst system containing such a component. It is related to.

(Prior art and its problems) Magnesium-containing supported catalysts with high catalytic activity and good stereospecificity have been developed, and it is easy to dispose of the catalyst residue in the produced polymer. It is well known that it is suitable for gas phase alpha olefin polymerization because it does not require removal of components.

Catalysts for gas phase alpha olefin polymerization are also required to have good particle shape, narrow particle size distribution, good crushing resistance, and high particle density in order to obtain good operability. There is. As one method for improving the morphology of these catalyst particles, as disclosed in JP-A No. 63-54,405, a magnesium compound is dissolved in alcohol in the presence of carbon dioxide, and then buried in IA with a mixture of titanium halide and organosilane to precipitate it. A method is described in which a well-shaped carrier is obtained by adding a cyclic ether compound, redissolving and recrystallizing, and activating the carrier to use it as a catalyst.

In gas phase alpha olefin polymerization, many copolymers are produced by taking advantage of the characteristic that the rubber component in the produced polymer does not leak into solvents. It is necessary to maintain good fluidity of the powder, and for this purpose the particle size of the polymerized powder must be large, and a catalyst component with a large particle size is required to produce such a powder. There is.

In general, with catalyst particles produced by the precipitation method from fI liquid, even if the carrier particles are clean and have a sharp particle size distribution, it is unavoidable that some of the particles will collapse during the subsequent activation treatment process, etc. Ta. In addition, the larger the particles, the more easily they break.
No. 405 also leaves room for improvement, as when the particle iY becomes large in size, such as 30μ, the amount of particles crumbling increases during the activation treatment with titanium halide, etc., and the amount of powder removed increases. Ta.

The present inventors used a specific silane compound, that is, an alkylsilane alkoxide, as a particle shape control agent during precipitation from a solution, and also added an alcohol during recrystallization by adding a cyclic ether compound. When making components, especially when making large particle catalysts, we have discovered a method for producing large particle supported catalysts in which the particles do not collapse or only slightly collapse during the titanium halide treatment. The invention relates to a method for producing this large-particle supported catalyst with a good crystal shape.

(Problems to be Solved by the Invention) The present inventors have discovered that while maintaining the high activity and highly stereoregular polymerization performance of the above-mentioned catalyst system, when controlling the catalyst from a small particle size to a large particle size, In particular, as a result of intensive research on methods for improving particle shape and particle size distribution at large particle diameters,
The present invention has been achieved, which makes it possible to obtain a large-particle supported catalyst with a sharp particle size distribution and a uniform shape while preventing particle crushing during the catalyst component manufacturing process.

That is, an object of the present invention is to provide a method for producing a supported catalyst having large particles with a sharp particle size distribution, high activity, and high stereoregular polymerization performance, suitable for olefin polymerization, particularly copolymerization in the gas phase. It is to be.

Means to solve problem C) The present invention has the following configuration.

(1) A catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, comprising: A. General formula Mg(OR'1n
Magnesium compound represented by (QR")z-n or MgR3゜(OR'+2-), or a mixture thereof■
(Here, R+42.R3 and R4 are an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group having 5 to 20 carbon atoms, and i and n are 0 ), carbon dioxide [
b] in the presence of. 1 carbon number represented by general formula R50II
20 saturated or unsaturated monohydric or polyhydric alcohols [c] are mixed in an inert hydrocarbon solvent and reacted and dissolved to obtain (component A), and B. (component A) and. Titanium halide represented by the general formula TiXp(OR7)na (where X is Cl or Br, R' has 1 to 1 carbon atoms)
20 alkyl group, aryl group or cycloalkyl group of carbon a3 to zO, p is 1 to 4) and/
or general formula VQX, ((IR'l s - vanadyl halide and/or general formula VX, (
OR7) Vanadium halide represented by 4-r (where X is Cl or Br, R' and R' are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a3
~20 cycloalkyl groups, q is 1 to 3, r is 1
~4) and/or general formula 5IXs (OR7
) Halogenated silane [d] represented by 4-1 (where X is Cl or 8r, RO is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, S is 1 to 4) and Si-0-Si
A siloxane compound having a bond or a mixture of the siloxane compound and a silane compound formed by the general formula R"7Si(OR")s-t (where RIORll is an alkyl group or aryl group having 1 to 20 carbon atoms) , or a cycloalkyl group having 3 to 20 carbon atoms, and rainbow is a cycloalkyl group having 0 to 3 carbon atoms.
is the number of C1 solid product (I). React with a saturated or unsaturated monohydric or polyhydric alcohol (■) having 1 to 20 carbon atoms and a cyclic ether (■) represented by the general formula R'20H,
A solid product (II) was obtained by dissolving and reprecipitating, and D. the solid product (11). General formula TiXp (OR
7) Titanium halide represented by 4-11 (here,
× is C1 or Br, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, p is 1 to 4) and/or general formula 5IXs (OR' Hanadyl halide represented by l 3-q and/or general formula VXr (0118) 4-r
Vanadium halide represented by
20 alkyl groups, aryl groups, or cycloalkyl groups having 3 to 20 carbon atoms, q is 1 to 3, and r is 1 to 4) (component B) [h] is reacted to form a solid product. A catalyst component consisting of a solid product (tV) obtained by reacting (component B) a mixture of (ITI) and an electron donor with (component B) [i].

(2) The catalyst component according to item 1 above, wherein the alcohol used in step C is a straight alcohol having 2 to 10 carbon atoms.

(3) A catalyst component for alpha olefin polymerization comprising a combination of the catalyst component described in item 1 above and an organometallic compound, or a combination thereof with an electron donor as a third component.

The configuration and effects of the present invention will be explained in detail below.

First, stage A will be described.

In step A, in the presence of carbon dioxide [b], the general formula vg(OR7)n(OR7)2-n or Mgn3m
(OR7) Magnesium compound represented by 2- or a mixture thereof [d] (where R1, R2, R3
, R4 is an alkyl group having 1 to 2a carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group having 5 to 20 carbon atoms, and m and n are numbers from O to 2. of. 1 to 2 carbon atoms represented by the general formula R5OH
0 saturated or unsaturated monohydric or polyhydric alcohol ■ in an inert hydrocarbon solvent and react and dissolve it (
Component A) is obtained.

The reaction can be carried out for 10 minutes to 24 hours at 10-200°C, preferably 20-tSO°C, but each raw material is immersed at room temperature of 10-30°C, and then at 40-15Q°C.
It is desirable to raise the temperature to a temperature of 100% to facilitate dissolution of the magnesium compound.

M as a magnesium alcoholate useful in the present invention
g(OCl1312. Mg(OC211s)2.
Mg(,OC:+Ht)2Mg(OC411J2.M
g(OClI(C1h)CzllsL, 2Mg(OCa
ll+7)2J(OClI2CH(C2If,)C41
1s)2. J(OClI, CHClI2)2Mg(
OCaHs)z, Mg(OCaL+L, Mg(
OCaH4(:lchild3)2Mg((JCloHv)z,
Mg(OC+oHa(:ll5)z, Mg(OCroH
+1)x.

Mg (OClOII16CH3)2. lJg(OC
lliHOCzHs), Mg(OC21+5)(OCa
H+, ), g (OC2Hi) (OCall+t
), Mg (OC3117) (OCaHs), and the like.

In addition, as alkylmagnesium, Mg (CL)
2.

Mg (C2H5) 2, Mg (C3Hs) 2. Mg
(C<He)z', Mg(CaH+3)z.

klg (C6H1712, Mg (CHCHC2H5
) m −'Ag (C1lH812Mg(C6J(:
113L, Mg(CaHr+)z, Mg(Cl.

H7)2Mg (C11,)fczus)J (CJs
) (C8H1t), Mg (C3H7) (CsHs), and mixtures thereof and Mg (OCJ
s) (C4H9), Mg(0(:5ly) (C
aHs) can also be used.

As the alcohol of component (2), aliphatic saturated and unsaturated alcohols can be used. Specifically, methanol, ethanol, propatool, isoproptool, isobutanol, tertiary butanol, octatool, 2-ethylhexanol, cyclohexanol,
Examples include dodecanol, propenyl alcohol, butenyl alcohol, as well as ethylene glycol, trimethylene glycol, etc., among which carbon atoms with 2 to 10 carbon atoms are used.
Preferred are aliphatic alcohols.

Next, in the next step, (component A) is added to 5t-0-5
A siloxane compound having a t bond or a mixture of the siloxane compound and a silane compound represented by the general formula R"tsi(OR")3-t (here, R10411 is
an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number from O to 3). General formula TiX* (OR'
3 a-p te represents titanium halokenide (here, X
is C1 or Cl or Br, R11 has 1 to 20 carbon atoms
an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, an aromatic group, p is 1 to 4) and/or a halogenated group represented by the general formula VOXq (OR'l, -q) vanadyl and/or general formula VX,
(OR8) Vanadium halide represented by a-r (
Here, X is Cl or Br, and R'Ra is an alkyl group having 1 to 20 carbon atoms, an allyl group, or 3 to 2 carbon atoms, respectively.
0 cycloalkyl group, q is 1-3, r is 1-4
) and/or general formula S iX, (OR9)
A solid product (r) is obtained by reacting with a halogenated silane [c] represented by J□.

This reaction is preferably carried out in an appropriate amount of an aromatic or aliphatic inert hydrocarbon solvent.

The mixing order for the reaction may be to mix (component A) and the siloxane compound, and then add titanium halide and/or vanadyl halide and/or vanadium halide; It is desirable to mix vanadyl halide and/or vanadium halide and add (component A) thereto.

The temperature during mixing can be from -40°C to 100°C, but preferably from -10°C to 50°C.

■ Siloxane compounds include hexamethyldisiloxane, hexaethyldisiloxane, hexabutyrodisiloxane, octamethyltrisiloxane, octaethyltrisiloxane, and others with the formula RzSi-(OSiR2).
A linear polysiloxane represented by n-OSiR, where R is an alkyl group, aryl group, cycloalkyl group, or aromatic group having 1 to 20 carbon atoms, and n is 1 to 10
polyalkylalkoxysiloxanes having alkoxy groups in part, such as hexamethyl-1,5-jethoxytrisiloxane, hexaethyl-1,5-dimethoxytrisiloxane, hexaethoxy-1,5-
Like dimethyltrisiloxane and octaethoxy-1,5-dimethyltrisiloxane. General formula R(RO)2s
i (OSi (OR) 2) n-0Si (ORI
Polyalkoxyalkylsiloxane represented by 2R, such as hexamethylcyclotrisiloxane and octaethylcyclotetrasiloxane. General formula (OSiR2). Examples include cyclic polysiloxanes represented by:

Furthermore, examples of silane compounds used in combination with these siloxane compounds include trimethylmonoethoxysilane,
Trimethylmonopropoxysilane, trimethylmonobutoxydisilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonobutoxysilane, tripropylmonoethoxysilane, tributylmonomethoxysilane, tributylmonoethoxysilane, trihexylmonoethoxysilane, cyclohexyl Dimethylmonoethoxysilane, dimethyljethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane,
Diethyldimethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, cyclohexylmethyljethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltributoxysilane, propyltriethoxysilane, butyltrimethoxysilane, Examples include allyltrimethoxysilane, allyltriethoxysilane, and the like.

Si/Si of the siloxane compound or the mixture of siloxane compound and silane compound used in step B and component A
The molar ratio of Mg is typically 0.1/1 to 2.0/, preferably 0.3/1 to 1/1.

The titanium halides represented by the general formula TIXo (OR6) J-11 in (2) include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride,
Propoxy titanium trichloride, butoxy titanium trichloride, hexoxy titanium trichloride, octoxy titanium trichloride, cyclohexoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, butoxy titanium tribromide, jetoxy titanium dichloride, Dipropoxy titanium chloride, dibutoxy titanium dichloride, dioctoxy titanium dichloride, diphenoxy titanium dichloride, dicyclohexoxy titanium dichloride,
Examples include jetoxytitanium tribromide, dibutoxytitanium tribromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, triphenoxytitanium bromide, etc. I can do it.

Titanium halides other than titanium tetrachloride and titanium tetrabromide can be produced by the reaction of titanium tetrahalide and orthotitanate, but instead of the product produced by this reaction, titanium tetrahalide and orthotitanate can be produced. Mixtures with titanate esters can also be used. Among these titanium halides, titanium tetrachloride is most preferred.

Also. General formula VOXq(OR7)3-Q, VXr(O
The vanadyl halides and vanadium halides represented by R'14-1t' include vanadyl trichloride, vanadyl tribromide, ethoxyvanadyl dichloride, butoxyvanadyl dichloride, phenoxyvanadyl dichloride, methoxyvanadyl tribromide, Propoxyvanadyl bromide, cyclohexoxyvanadyl tribromide, dimethoxyvanadyl chloride, jetoxyvanadyl chloride, dicyclohexoxyvanadyl chloride, dipropoxyvanadyl bromide, dibutoxyvanadyl bromide, vanadium tetrachloride, vanadium tetrabromide, trichloride Methoxyvanadium, ethoxyvanadium tribromide, butoxyvanadium trichloride, cyclohexoxyvanadium tribromide, phenoxyvanadium trichloride, jetoxyvanadium dichloride,
Examples include dibutoxyvanadium tribromide, phenoxyvanadium chloride, trimethoxyvanadium chloride, triethoxyvanadium bromide, tripropoxyvanadium chloride, tributoxyvanadium bromide, and triphenoxyvanadium chloride.

Examples of the lerhalokenated silane [c] represented by the general formula 5tXs (f) R11) 4-@ include silicon tetrachloride, silicon tetrabromide, methoxy silicon tribromide, ethoxy silicon trichloride, propoxy silicon tribromide, and trichloride. Butoxy silicon, cyclohexoxy silicon trichloride, dimethoxy silicon dichloride, jetoxy silicon tribromide, dipropoxy silicon dichloride, dibutoxy silicon tribromide, diphenoxy silicon dichloride, trimethoxy silicon bromide,
Examples include triethoxy silicon chloride, tripropoxy silicon bromide, tributoxy silicon chloride, and the like. Moreover, a mixture of these can also be used.

The molar ratio of the total number of moles of metal of titanium halide or/and vanadyl halide or/and vanadium halide or/and halogenated silane used in step B to J of component A is preferably from 1703 to 20/I. is 1105 to 5/1.

In step C, the solid product (I) is converted into a cyclic ether ■
The solid product (
Obtain [I]. By dissolving the entire amount and re-precipitating it, a carrier (solid product (II)) having a uniform particle shape and particle size can be obtained. In the precipitation mother liquor of stage C,
The mother of step B is prepared by adding alcohol to a suspension in which the siloxane compound ■ is present and containing the solid product Cl> followed by the addition of the cyclic ether ■, or by adding the cyclic ether compound along with the alcohol. A large particulate support (solid product (U)) is obtained.

The temperature during the addition of the alcohol and the cyclic ether is -40 to 100°C, preferably -10 to 50°C, and the temperature after addition is from 1 minute to 10 hours, preferably from 5 minutes to 5 hours't'50
The temperature is raised to ~150°C and maintained at this temperature for 1 minute to 6 hours, preferably 5 minutes to 3 hours, to complete the precipitation.

Examples of the cyclic ether [g] include tetrahydrofuran, tetrahydrofilane, methyltetrahydrofuran, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, diochitin, dioxolane, trioxane, biran, benzobylane, dihydrobenzofuran, and the like.

Among them, Tetora Shidorofuran is the best.

Alcohols include straight alkyl alcohols such as methanol, ethanol, normal propatool, isopropanol, butanol, isobutanol, tertiary butanol, pentanol, hexanol, 2-ethylhexanol, octatool, and cyclopene. Examples include cyclic alkyl alcohols such as tanol and cyclohexanol, diols such as 1,2-propanediol and 1,4-butanediol, ethylene glycol, trimethylene glycol, and propenyl alcohol and butenyl alcohol. .

Among them, ethanol, propatool, isoprobanol, butanol, 2-ethylhexanol, etc. with a carbon number of 2
~IO straight alkyl alcohols are best.

In stage vaD, a solid product (1■) is produced. General formula r
Titanium halide represented by txp(R7)4-P and/or vanadyl halide represented by general formula VOXq(OR7) and/or general formula VX, (
OR7) Component B consisting of vanadium halide represented by 4-r [h] is reacted to form a solid product (III
”) (where X is Cl or Br, R', R
7, R6 is an alkyl group having 1 to 20 carbon atoms, an allyl group, or a cycloalkyl group having 3 to 20 carbon atoms, q is 1 to 3, p and r are 1 to 4), and (Component B) Solid product (IV) is obtained by reacting a mixture of [i] and electron donor [j].

Component B here can be selected from among titanium halides, vanadyl halides, or vanadium halides as explained in step B. solid product (
II), (III) and component B may be mixed by adding component B to the solid product (+1), (Ill) or by immersing the solid product (II), (Ill) into component B. .

The treatment temperature for the solid product (II) and (III) in each step is 40 to 200°C, preferably 50 to 150°C.
℃, and the reaction time is 5 minutes to 6 hours, preferably 10 minutes to 5 hours.

After the reaction, solids are separated by filtration or decantation, and then washed with an inert hydrocarbon solvent to remove unreacted substances or by-products. The cleaning effect can be further improved by cleaning with an aromatic solvent such as toluene, benzene, or xylene before cleaning with an inert hydrocarbon solvent.

Suitable electron donors for this treatment are aromatic and polycarboxylic acid esters.

Examples of the aromatic polycarboxylic acid ester include benzene polycarboxylic acid ester and naphthalene polycarboxylic acid ester.

Specifically, the benzene polycarboxylic acid esters include monomethyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
Ditert-butyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-phthalate
-octyl, diphenyl phthalate, dibenzyl phthalate, etc.; examples of aromatic monocarboxylic acid esters include methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl henschede, cyclohexyl henschede, methyl p-toluate, ethyl-1 )-toluate, methyl p-anisate, butyl p-anisate, ethyl chlorohenshade, methyl bromobenzoate and other benzoic acid esters and benzoic acid esters having substituents.

The electron donor used in the step is used in an amount ranging from about 0.0001 to 1.0 mole per titanium or vanadium duram atom, preferably from 0.000 to 0.08 mole per gram atom.

Diluents useful in the present invention include aromatics such as benzene, toluene, xylene, ethylbenzene, halogenated aromatics such as chlorobenzene, dibromobenzene, hexane, heptane, octane, nonane, decane, undecane, cyclohexane. , alkanes Q such as methylcyclohexane, halogenated alkanes such as 1,2-dichloroethane, lj, 2-trichloroethane, carbon tetrachloride, isoparaffinic hydrocarbons, kerosene, and the like.

The catalyst components are prepared under an atmosphere of an inert gas such as nitrogen or argon gas or an alpha-olefin atmosphere, excluding catalyst poisons such as water and oxygen-carbon oxides. Also, purifying the diluents and raw materials used will help remove catalyst poisons from the catalyst production system as a result of the above-mentioned preparations.
A solid product (1
v) is obtained.

〔Effect of the invention〕

The effect of the present invention is that it is possible to produce a catalyst with a large particle size for polyolefin polymerization while maintaining a good crystal shape, and the particles do not collapse or collapse during the manufacturing process. Since the amount of carbon dioxide is extremely small, it is possible to produce large particle catalysts with a sharp particle size distribution.

Large particle catalysts with a sharp particle size distribution retain their large shape as a replica of the polymer produced during polymerization, so even if the polymer becomes sticky polymer particles, its fluidity is lower than that of small particles. This dramatic improvement is well known among our experts, and this makes it extremely useful for producing copolymers with high rubber component content by gas phase polymerization with good operability. There is.

Example 1 Step A Formation of magnesium carbonate solution 2308 magnesium ethoxide was placed in a 3L autoclave equipped with an old pressure gauge and thermometer and purged with high purity nitrogen, and 41511J2 2-ethyl-1-hexanol was added. and 165Qa+Il of toluene were added.

The mixture was heated at 90° C. for 3 hours with stirring at 5 GO rpm under 2 kg/cw”c of carbon dioxide.

The resulting solution was cooled, purged of carbon dioxide gas, and handled primarily under atmospheric pressure. The solution contained 0.1 B/mu of magnesium ethoxide.

Step B Formation of solid particles L500+Ij2 baffled flat bottom flask with stirrer, thermometer, condenser and nitrogen sil line (
Toluene 300sj2 into the baffle ratio 0.15),
TiCj24 19aJ2 and hexamethyldisiloxane 25IIIL were added and mixed at 300 rpm for 5 minutes at room temperature, and then 150+mJ2 of the solution of Step A was immersed in for 10 minutes. Immediately after charging, solid particles (1) precipitated.

Step C Reprecipitation of Solid Particles To this, 3 Ili of ethanol and 50 mA of tetrahydrofuran (THF) were each added using a syringe. Stirring was maintained at 3Q rpm and the temperature was raised to 60°C within 15 minutes. The precipitated particles dissolved in the TIIF solution and began to precipitate again within 15 minutes, and solid formation was complete within 10 minutes. After stirring was continued for 45 minutes at 60° C., stirring was stopped and the formed solid (1 inch) was allowed to settle. The supernatant liquid was removed by decantation, and the remaining solid (II) was washed twice with 200 g+1 toluene.

Step D Titanium(IV) Compound Treatment Step C solid (n) is treated with 200 μl of toluene and 100 μl of toluene.
TiCj14 of ajl was added. The temperature was raised to 135° C. within 20 minutes while stirring at 600 rpm, and this temperature was maintained for 1 hour. Stop stirring and form solid (III)
was allowed to settle, and the supernatant liquid was removed by decantation.

100 III of Tit, Q, 250 Ilf of toluene, 2.111 ff of diisobutyl phthalate were added to the product solid (Ill) and the mixture was heated to 60 Orpm.
, and stirred at 135°C for 1.5 hours. The supernatant liquid was removed by decantation.

20011J2 (7) Add T1Cu, 600
Reflux by heating for 10 minutes while stirring at rpm''c. Remove the supernatant liquid by decantation!, add 200ml of toluene 3 times, and then add 2QOou of hexane 4 times.
Washed twice.

A total of 11.6 g of solid product (tV) was recovered.

This solid product (IT) has an average particle size of 372μ, 0.2% fine powder less than 5μ, and its analytical values are 17.3% magnesium, 2.3% titanium, 55.6% chlorine, and Di-n-butyl phthalate was 8.6%.

Gas phase polymerization In a stainless steel reactor with an internal volume of 3 L and equipped with a multi-stage stirrer, which was purged with nitrogen, 2.01 ml of triethylaluminum, 0.3 v Amol of diphenyldimethoxysilane, and the solid product (
IV) to 16. After adding 8L of OB and hydrogen, 7
Polymerization was carried out at 0°C for 2 hours while continuously introducing propylene so that the total pressure was 22 kg/cn"G. After that, unreacted propylene was discharged and powdered propylene 3
82g was obtained. Most of the particles of the polypropylene were crystalline in the form of inclined hexagonal columns. The residual ratio of the polymer after 6 hours of extraction with boiling 11n-hexane was 0.8%, and the bulk density was 0.48 g 7 cm''.

Example 2 Using solution 150LaJ2 from Step A of Example 1, Step 1i
In step 1B, 100 sJ2 toluene, 1 Ohi chlorobenzene, 32 to 1 part hexamethylcyclotrisiloxane were used, in step C, 40all THF was used, and in step 200 sJ2 TiCl2 during the third TiCJ24 treatment. ．． as a solvent 12
12. Repeat Example 1 except for closing the image at 5°C for 1 hour.
7g of solid product (1v) was obtained. Solid product (IV)
The average particle size of is 30.5μ, and particles smaller than 5μ are 0.5μ.
It was 7%.

Example 3 An IL autoclave was used for the reaction after step B, and 170 vIl of the solution from step A of Example 1 was used for each step, and 20
0-ρ toluene, 28mj2 hexamethyl 1.5
- using jetoxytrisiloxane, in step C,
Step B to Step C using THF of 701111 with stirring at 400 rp @ I Kg/cm”G
Example 1 was repeated except that 2.1 i of diisobutyl phthalate was used instead of di-n-butyl phthalate in the second rtctta'A process of the step. Ta. Solid product (I
The yield of V ) was 21.0 g, and the average particle size was 33.2
Particles with a particle size of 5 μ or less were 1.8%. The analysis values of the solid product are: Mgla, 3%, Ti 2.5%, C
159% and diisobutyl phthalate 7.8%.

Example 4 Using the solution/&15011j2 of Step A of Example 1, 15
Using 0■j2 of toluene, 501J2 of chlorobenzene, and 36ail of octaethoxy-1,5-dimethyltetrasiloxane, stage l! In IC, 60
Example 1 was repeated except using -ρ THF. The average particle size of the solid product (1v) is 25.3μ;
The proportion of particles smaller than 5μ was 0.2%.

Example 6 In Step A, 286 g of magnesium propoxide was used instead of magnesium ethoxide, and 3[13
Example 1 was repeated except that 1J2 of 2-ethyl-1-hexanol was used to obtain 12.2 g of solid product HV). The average particle size of the solid product (IV) was 27.5μ, with 1.2% of particles smaller than 5μ.

Example 5 In the steps of Example 1, 114 mj of solution in step A!
using 1401Ii toluene, 6hJ2 (7) isoparaffin (Isopar G), 14i T1Cu
4.1 using 22af hexanemethyldisiloxane
, in step C, TiCl24 treatment in stages was performed in two stages using 27IIIl of THF, and the third T1
Cf.

Example 1 was repeated except that no washing was performed to obtain 10.6 g of solid product (IV). The average particle size of the solid product (rV) is 22.8μ, and particles smaller than 5μ are 0.5%
Met.

Example 7 Stirrer, thermometer, condenser, nitrogen seal line,
It has a raw material feed line, a heating jacket and
IL of toluene, 200 liters of toluene was placed in a 5 L stainless steel reactor with 4 flat baffles inside (Baffle! i! 0.15).
-1 hexamethyldisiloxane, 10G-1 TiC
After adding lt4 and stirring for 5 minutes at room temperature and 120 rpm, 750 sJ2 of the solution in step A of Example 1 was added for 30 minutes. After adding 250 ml of THF and increasing the stirring speed to IBO rpm, the temperature was raised to 60° C. within 15 minutes and maintained at this temperature for 45 minutes.

The slurry after the reaction was sent under a nitrogen seal to a 5L filtration device equipped with a stirrer, a condenser, a thermometer, a nitrogen seal line, a heating jacket, and a filtration unit at the bottom. 2
Washed twice.

50011IIl of TiCl4.500aj! to the solid product (II) in the filter. Add toluene to 135℃
, and kept at 180 rpm for 1 hour. After filtering this,
5QOmiL TiCl4.1G, 5mJ2 Jean n-
Butyl phthalate and IooomIL toluene were added, and the mixture was kept at 135°C for 15 hours in LHrpII, and then filtered.

To the solid product (■), 1,000 ugly 1 of TiCl14 was further added, heated and refluxed for 10 minutes, filtered, and
Washed three times with 00aIL of toluene and an additional four times with 500aIL of hexane. The solid product remaining in the filter (IV
) was dried with hot nitrogen gas at around 60°C,
82.2 g of catalyst was obtained.

The analysis values of the solid product (ff) were: Mg 18.7%;
II: 2.6%, C: 6.2%, di-n-butyl phthalate: 6.2%. The average particle size of the solid product (tV) was 45.1μ, and particles smaller than 5μ were 0.4%.

Comparative Example 1 In step B of Example 1, 11.7 g of solid product (IV) were obtained according to the entire procedure of Example 1, except that no alcohol was used. In this case, stage C
Sedimentation for step-by-step decantation took a long time, and some fine particles were lost. Further, the amount of fine powder of 5μ or less in the obtained solid product (IV) was 45%.

Gas phase polymerization of propylene was carried out in the same manner as in Example 1 except that the obtained solid product (IV) was used.

Comparative Example 2 Example 1 was repeated except that in stage 51B of Example 1, neither siloxane compound nor alcohol was used, yielding 12.3 g of solid product (IV).

Particles smaller than 5μ in the solid product (tV) were 39.2%.

Gas phase polymerization of propylene was carried out in the same manner as in Example 1 except that the obtained solid product ([V 2 ) was used. The obtained polymer particle size distribution is shown in Table 1 together with the results of Example 1 and Comparative Example 1.

Comparative Example 3 Example 4 was repeated except that in step B of Example 4, 20×1 trimethylchlorosilane was used instead of the siloxane compound.

Gas phase polymerization evaluation Using the solid products (IV) obtained in Examples 2 to 7 and Comparative Examples 1 to 3, gas phase polymerization was carried out in the same manner as in Example 1. The results are shown in Table 2.

Example 8 In step B of Example 1, dimethyljethoxysilane 10IIJ2 with hexamethyldisiloxane 2012
Example 1 was repeated except that the solid product (I
V) 12.9g was obtained. The average particle size of the solid product (1v) was 352μ, with 2.0% particles smaller than 5μ.

Example 9 Example 1 was repeated, except that in step C of Example 1, instead of using 50 LIJ2 of THF, 60 sJ2 of tetrahydropyran was used to obtain IQ, 9 g of solid product (IV). The average particle size of the solid product (n/l) was 21.9μ, with 6.3% particles smaller than 5μ.

Example 1O In step C of Example 1, instead of the 25@a hexamethyldisiloxane, the viscosity of 32 ρ was 10c.
Using 50 mft of T dimethylpolysiloxane,
Example 1 was repeated, except that 6011 2-methyltetrahydrofuran was used instead of HF, yielding 13.1 g of solid product (rV). The average particle size of the solid product (IV) was 298μ, with 27% particles smaller than 5μ.

Comparative Example 4 Example 9 except that in step B of Example 9, hexamethyldisiloxane and alcohol were not used.
This was repeated to obtain a solid product (IV) of 1Q, sg.

The solid product (IV) contained many fine particles, with 29.7% of particles having a size of 5 μm or less.

Comparative Example 5 Example 1O was repeated except that in stage 1!11B of Example IO, no siloxane compound was used;
3.6 g of solid product (IV) was obtained. Solid product (I
V) contained many fine particles, with 11.3% of particles having a size of 5μ or less.

Slurry Polymerization Evaluation Using the catalysts obtained in Examples 8 to 10 and Comparative Examples 4 to 5 (solid product Hv), hexane slurry polymerization of propylene was carried out.

1. Take 10hJ2 of hexane in an SL autoclave, add 100ml of TEA 2, 0.2mmol of diphenyldimethoxysilane. Add 17@g from catalyst 15B, introduce 6[1ijl of hydrogen, and increase the pressure to 7 Kg/g with propylene.
cm"G, 7Dt: After completing one reaction of polymerization for 2 hours, purge the monomer gas, add 50 g of methanol, stir for 10 minutes at 70°C, filter, dry the polymer, and use the catalyst. Polymer yield per volume was calculated.

The polymer dissolved in hexane was recovered from the filtrate. The results are shown in Table 3.

Example 11 Bulk polymerization was performed using the catalyst obtained in Example 2.

Phenyltriethoxysilane [1.3 gmol, 9 mg of catalyst, and 300 sjl of hydrogen were immersed in an IL bulk polymerization vessel together with 5 GGg of propylene.
Polymerization was carried out at 0° C. for 30 minutes at 35 kg, 76 plates, and 2 G. Purge unreacted propylene monomer and dry powder 227
I got g. Polymer yield per gram of catalyst is 25.300
g, the extraction content by 6-hour hexane reflux is 0.8%, and the apparent density of the polymer is 0.49 g/cm.
It was 3.

Propylene-ethylene copolymerization was carried out at 70° C. and 22 g/cm”G for 1 hour by introducing a mixed gas of

Example! 2 Using 10s+g of the catalyst obtained in Example 7, Example 1 [
After carrying out bulk polymerization for zO minutes in exactly the same manner as above, unreacted propylene was purged and propylene/ethylene! Gas phase polymerization was carried out at 70°C and 18 kg/ca"G for 30 minutes by introducing a 2/1 mixed gas and 150 x 1 hydrogen gas. The yield of the polymer was 187 g, and the ethylene content in the polymer was 11. It was 5%.

Example 13 15 mg of the catalyst obtained in Example 7 was added to the polymerization vessel of Example 1.
, TEA 2 mmal, diphenyldimethoxysilane 0.2 mol, hydrogen 150 mj! is absorbed by propylene monomer, propylene/ethylene-4/1
Table 1 Gas phase polymerization polymer particle size distribution table

[Brief explanation of drawings]

Figure 1 shows Explanation of the method for producing the catalyst component of the present invention This is a manufacturing process diagram (flow sheet) for Below Up Special permission Out wish Man Chisso Corporation

Claims (3)

[Claims] (1) A catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, General formula Mg(OR^1)_n(OR^2)_2_-
Magnesium compound represented by _n or MgR^3_m(OR^4)_2_-_m or a mixture thereof [
a] (Here, R^1, R^2, R^3, R^4 are alkyl groups having 1 to 20 carbon atoms, aryl groups, or 3 carbon atoms
20 cycloalkyl group or 5 to 2 carbon atoms
0 aromatic group, and m and n are numbers from 0 to 2), in the presence of carbon dioxide [b], a saturated or unsaturated group having 1 to 20 carbon atoms represented by the general formula R^5OH B. mixed with monohydric or polyhydric alcohol [c] in an inert hydrocarbon solvent and reacted and dissolved to obtain (component A); B. (component A) and the general formula TiX_p(OR^6)_
Titanium halide represented by 4_-_p (where, 1 to 4) and/or general formula VO
Vanadyl halide represented by X_q(OR^7)_3_-_q and/or general formula VX_r(OR^8)_
Vanadium halide represented by 4_−_r (where,
X is Cl or Br, and R^7 and R^8 are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or 3 to 2 carbon atoms.
0 cycloalkyl group, q is 1-3, r is 1-4
) and/or the general formula SiX_s(OR^9)
_4_-_s halogenated silane [d] (where X is Cl or Br, R^9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms) , s is 1 to 4) and Si-O-S
A siloxane compound having an i bond or the siloxane compound and the general formula R^1^0_tSi(OR^1^1)_
3_-_t mixture with silane compound [e](
Here, R^1^0, R^1^1 are carbon numbers from 1 to 20
(C. The solid product (I) is a saturated or unsaturated monohydric or polyhydric alcohol having 1 to 20 carbon atoms represented by the general formula R^1^2OH [f] and a cyclic ether [g]
D. to obtain a solid product (II) by dissolving and reprecipitating. The solid product (II) has the general formula TiX_p(OR^
6) Titanium halide represented by_4_-_p (where X is Cl or Br, R^6 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, p is 1 to 4) and/or vanadyl halide represented by the general formula VOX_q(OR^7)_3_-_q and/or the general formula VX_r(OR^
8) Vanadium halide represented by_4_-_r (where, is an alkyl group, q is 1 to 3, r is 1 to 4) (component B) [h] is reacted to obtain a solid product (III), to which (component B) [i] catalytic component consisting of a solid product (IV) obtained by reacting a mixture of and an electron donor [j]. (2) The catalyst component according to claim 1, wherein the alcohol used in step C is a linear alcohol having 2 to 10 carbon atoms. (3) A catalyst component for alpha olefin polymerization comprising a combination of the catalyst component according to claim 1 and an organometallic compound, or a combination thereof with an electron donor as a third component.