JPH01118504A - Drying of catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the above catalyst component without formation of large particles, by suspending or mixing a catalyst component for polymerizing olefins contg. Ti, Mg, and halogen in a specified liq. hydrocarbon and drying it. CONSTITUTION:A catalyst component (A) for polymerizing olefins obtd. from an essential component consisting of an Mg compd. (a), a Ti compd. (b) whose molar ratio to the component (a) is 1X10<-4>-1,000 and a halogen (c) whose molar ratio to the component (a) is 1X10<-2>-1,000, if necessary, an Si, Al or B compd. (d) whose molar ratio to the component (a) is 1X10<-3>-100 and an electron donating compd. whose molar ratio to the component (a) is 1X10<-3>-10 is suspended or mixed in 1-100ml, per g of the component A, or a liq. hydrocarbon (e.g., n-heptane) contg. 0.01-10g per g of the component A of sufficiently purified polyolefin particles (e.g., polyethylene) whose average particle size is 100-1,000mu and the mixture is then dried under a pressure of 1-700mmHg at 0-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for drying catalyst components for olefin polymerization. j1! More particularly, the present invention relates to a method for drying a catalyst component that enables the production of a polymer with high activity and good polymer properties when applied to the polymerization of olefins.

BACKGROUND OF THE INVENTION Conventionally, when handling, storing or preserving, and transporting catalyst components for olefin polymerization, there are broadly two types of methods for preserving catalyst components. One is to slurry it in an inert solvent, such as a liquid hydrocarbon, and the other is to dry it, essentially free of solvent.

The former method often has problems with storage and transportation of catalyst components, and improvements are desired. - The latter method can solve the problem of party i, but it usually creates a new problem. This is because when the catalyst component is dried, aggregation tends to occur, resulting in the formation of coarse particles of the catalyst component.

When these coarse particles are generated, various problems occur, such as a decrease in catalyst activity, deterioration in polymer properties, and clogging in catalyst and polymer lines and valves. Therefore, it is desired to develop a drying method that does not cause the above-mentioned problem of graininess.

Prior art As prior art, %Kai No. 55-135105;
Publications such as No. 6-136805 and No. 62-50308 are cited. These prior art techniques claim that by leaving a small amount of liquid hydrocarbon or high-boiling point liquid hydrocarbon in the catalyst component, a catalyst component with high performance can be obtained without problems such as storage stability. However, these methods are not considered to provide a sufficient solution to the problem of coarse particles generated during drying, and new techniques are required.

SUMMARY OF THE INVENTION The present invention involves suspending an olefin polymerization catalyst component containing titanium, magnesium, and halogen as essential components into a liquid hydrocarbon containing polyolefin powder having an average particle size within the range of 100 to 1000 microns. The present invention provides a method for drying a catalyst component for olefin polymerization, which is characterized in that it is dried after being cloudy or mixed.

Effects of the Invention According to the method of drying a catalyst component for olefin polymerization of the present invention, it is possible to prevent the formation of coarse particles due to agglomeration of the catalyst component, which tends to occur during drying. As a result, the following effects are observed.

(a) There is no deterioration in catalyst performance due to drying. For example, there is no decrease in Tj8 in terms of catalyst activity, polymer properties, stereoregularity in polymerization of propylene, etc.

(b) Good operational stability during polymerization. Coarse particles of the catalyst component often produce coarse polymers during boat fishing, resulting in problems such as polymer adhesion on lines and in the pulp polymerization tank. According to the drying method of the present invention, all of these problems can be solved. Of course, it goes without saying that problems similar to those described above caused by the coarse catalyst particles themselves can be solved.

Detailed Description of the Invention (Catalyst Component) The olefin polymerization catalyst component used in the present invention is a solid component containing titanium, magnesium, and halogen as essential components. Here, "containing as an essential component" means that the plant may contain other elements for a purpose in addition to the three components of the plant, and each of these elements may exist as an arbitrary compound for a purpose. This indicates that these elements may exist in combination with each other.

Such solid components are known. For example, JP-A-53-45688', JP-A-54-3894, JP-A-54
-31092, 54-39483, 54-94
No. 591, No. 54-118484, No. 54-1315
No. 89, No. 55-75411, No. 55-90510, No. 55-90511, No. 55-127405, No. 55-147507, No. 55-155003, No. 5
No. 6-18609, No. 56-70005, No. 56-7
No. 2001, No. 56-86905, Mukai 56-9080
No. 7, 1lffJ No. 56-155206, No. 57-3
No. 803, No. 57-34103, No. 57-92007
No. 57-121003, No. 58-5309, No. 58-5310, No. 58-5311, No. 58-87
No. 06, No. 58-27732, No. 58-32604, No. 58-32605, No. 58-67703, No. 5
No. 8-117206, No. 58-127708, No. 58
-183708, 58-183709, 59-
Those described in each publication such as No. 149905 and No. 59-149905 are used.

Examples of the magnesium compound serving as the magnesium source for the solid catalyst component used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, etc. can be given.

Further, the titanium compound serving as a titanium source is a tetravalent titanium compound, and has the general formula Tl (OR")4-nXn (where R' is a hydrocarbon residue, preferably having 1 to 1 carbon atoms.
10, X represents halogen, and n is 0≦
Shows the number 4. ) can be mentioned. A specific example is TicA! ,,Ti 13r,,Tt
(oc, u, )C13,TI (OC*H3)1CJ
2,'rt(oc,H,)sC7%Ti(0-ic
,Ht)C13,Ti(0-nC4H,)C1s,Ti
(0-nC4H,), CJ,, Ti(QC2H,)
Br,,Ti(OC2H,)(OC4H9),CJ,
Ti (0-nc4H,), C7% Ti (0-C,)
I,)CI,,'l't (0-IC4Hs)*Cll
3,TI (OCIH1□)Cj,,Ti (OCs
H + m) CJs, Ti (OCJs) i Ti (0-nc1
H7) I'l't (0-"C4H@)4% Ti
(0-IC4Hs)4%TI(0-nesHti)a
s Tl(OncgH17) i'rt(ocn.

There are CH(CIH5) CA@)a, etc.

Furthermore, a molecular compound obtained by reacting TiX'4 (herein, X' represents a halogen) with an electron donor described later can also be used. Specific examples include TiCl4・CH, CO
C, f(i Ttcz4・CHa CO□C, Hi11
%t C71,・06 mountain NO□, TiCl4・CH,
C0Cj, TiC4・C,)i.

C0CJ, TiCJ, -C,H,C02C,H,%
'1"i(J, -CICOC, HTiCl4・C4
Examples include H, 0, etc.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but it may also be supplied from known halogenating agents such as aluminum halides, silicon halides, and phosphorous halides. Monkey too.

Halogens contained in catalyst components include fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred.

In addition to the above essential components, the solid components used in the present invention include 5ic
lca, 5icz, silicified adducts such as methylhydrodiene polysiloxane, Az (o-ic, H,),
ecls, A/Br,, AlC0C5Hs)s, Al
Aluminum compounds such as C0CHs)2C1 and B (
0CHj) g, B(OCs& )iB(OCsHs)
It is also possible to use other components such as boron compounds such as s, and there is no problem with these remaining in the solid component as components such as silicon, aluminum, and boron.

Furthermore, when producing this solid component, it is also possible to produce it using an electron donor as an internal donor.

Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid Examples include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) 1 to 18 carbon atoms such as methanol, ethanol, furopanol, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and inpropylbenzyl alcohol; Alcohol L C) 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, etc.
(3) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; (2) carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and nathaldehyde; Aldehydes of numbers 2 to 15, (
e) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate,
Ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, chlorha methyl, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, 7-enyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
2 to 2 carbon atoms such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, r-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
0 organic acid esters, (f) inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane, (t) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid Acid halides having 2 to 15 carbon atoms such as chloride, phthaloyl chloride, and phthaloyl inochloride; (3) C2 to 20 acid halides such as methyl ether, ethyl ether, inglovir ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether;
ethers, (su) acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine,
Examples include amines such as piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as [l]acetonitrile, benzonitrile, and tolnitrile.

These electron donors can be used in amounts of 2 or more.

The amount of each of the above components to be used may be any amount as long as the effect of the present invention is recognized, but for boat fishing, it is preferably within the following range.

The amount of the titanium compound used is I x 10-' to 1000 in molar ratio to the amount of the magnesium compound used.
It is preferably within the range of 0.01 to 10. When using a compound for that purpose as a halogen source, the amount used is I in a molar ratio relative to the amount of magnesium used, regardless of whether the titanium compound and/or magnesium compound contains a halogen.
X is preferably in the range of 10-” to 1000, preferably 0
．． It is within the range of 1 to 100. The amounts of silicon, aluminum and boron compounds to be used are in a molar ratio of I x 10-'' to 100 to the amount of the above magnesium compound used.
It is preferably within the range of 0.01 to 1.

The amount of the electron-donating compound to be used is preferably in the range of I x 10-'' to 10, preferably in the range of 0.01 to 5 in molar ratio to the amount of the magnesium compound used.

The above-mentioned solid catalyst component is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and further, if necessary, other components such as an electron donor.

(a) A method of bringing magnesium halide and, if necessary, an electron donor and a titanium-containing compound into contact.

(b) A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide, an electron donor, and a titanium/halogen-containing compound.

(c) A method of contacting a titanium halogen compound and/or a silicon halogen compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound.

As this polymer silicon compound, those represented by the following formula are suitable.

(Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
Fi indicates a degree of polymerization such that the viscosity of this polymeric silicon compound is on the order of 1 to 10 centistokes) Among these, methylhydrodiene polysiloxane, ethylhydrodiene polysiloxane, 1,3,5
,7tetramethylcyclotetrasiloxane,1,3,5
, 7.9 pentamethylcyclopentasiloxane, phenylhydrodiene polysiloxane, and cyclohexylhydrodiene polysiloxane are particularly preferred.

(d) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound.

(e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the compound as necessary.

(v) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.

As the catalyst component for olefin polymerization used in the present invention, the solid component obtained as described above can be used as it is, or the solid component can be prepolymerized by contacting it with olefins in the presence of an organoaluminum compound. It can also be used as

In the case of prepolymerization, there are no particular restrictions on the prepolymerization conditions, but the following conditions are preferred for boat fishing. The polymerization temperature is 0 to 80°C, preferably 10 to 60°C.
It is. As for the amount of polymerization, it is preferable to polymerize 0.001 to 50 grams of olefins, more preferably 0.1 to 10 grams of olefins per gram of the above-mentioned solid catalyst component.

Generally known organic aluminum components can be used during prepolymerization.

As a specific example, Al(c, Hs) and Aj(i80c4
H,) AI (CsHlm) AI (C, H□7)
Aj (Cs.R21)3, AI (C2H4)*
CI XAt (l5OC4H@) 2 CI X
Al(C211s)2H%AJl(tsoC,
H, ), H, AAI(CzHs)* (OC2H5), etc.

Among these, preferably AI(CzHs)s,
”(”0CaH*)x. Further, a combination of trialkylaluminum and alkyl aluminum halide, a combination of trialkylaluminum, alkyl aluminum halide, and alkyl aluminum ethoxide, etc. are also effective.

To give a concrete example 'x, Ajl(CzHs)s and AJI(C
2f(,), cl combination, AJI! (1soC4H4)
, and A1 (iso C4H9) 2 C1 combination, A
ocziis)s and AICC*Hs) 8.5c18. s
combination of hlccsH*)s and AIt(CsHs)*C
Examples include the combined use of z and AI (ext(s)a(QC, H,)).

The amount of organoaluminum component used during prepolymerization is AJ/Ti (molar ratio) of 1 to 20. Preferably it is 2-10. In addition to these, known electron donors such as alcohols, esters, and ketones can also be added during prepolymerization.

The olefins used in the prepolymerization conditions include ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
Examples include pentene-1. It is also possible to coexist with a prepolymerization condition element.

In this way, an olefin polymerization catalyst component containing titanium, magnesium and halogen as essential components is obtained.

In the method of the present invention, during the production of the catalyst component for olefin polymerization containing titanium, magnesium, and halogen as essential components obtained as described above, the general formula R"m however,
R' and R3 are hydrocarbon residues, X is a halogen, m and n are 0≦m≦3 and O≦n≦, respectively.
3, and 0≦m+n≦3).

Here, H''h and R4 are each preferably about 1 to 20, preferably about 1 to 10, hydrocarbon residues. X is preferably chlorine, at least from the economic point of view.

Specific examples include (CHx)Si(OCHs)n, (C
H3) 5' (OCIHs)m, (CzH
s)as' (OCHs)i, (n-C, Hll
)Sl(OCHs)I(CzHs)Sl(OCxHs
)s, (n-C8゜f(2□)Si(0C2Hs)s
, (CH,=CH)Si (OCR,)m, (J(CH
2).

5i(OCHL),, 5i(OCHL), 5t(QC2
H,)3CJ, (CzHs)2 S' (QC1 mountain) 2, (CryHas) 81 (OCH3)x, 5
i(0(,H,)i (Cabs)Si (OCHa)
81 (OCH3)2C6, (Colds)2Si
(OCHi)z, (CsHs) (CH3)5i(OC
Hs)*, (caHs)Si(OCzHi)3, (C6
[(,)2Si(QC!f(S)2,NCCCHz)2
Sj (OCxHs)s, (tl-C, ni■t)S
1 (0C2Hs) s, (CR3) S 1 (
QCsHt)s, (C,H,)(C1(2)Si
(0CaHs)(CHs)l C81(CH3)
(0CHj)z, (CE■,), C3i(HC(CH
s ) x ) (0CHs) 2, (CH,),
csi(cix,)(OC,H,),,(CiHs)s
C8I (CH3) (OCHa)z, (CH3)
(C,H,)CH-8i (CHI) (OCHa)z
, ((C1,)x CHCH2)81 (OCH3)2
,CzHsC(CHs)zsi(caj)(OC
Hn)z, C1)1. C(CHI > , S i (
CHi ) (OCzHs)z, (CHx)s CS
i(0CHa)s,(CL)sCS1(QC
2)15) s, (C2H5) s CS 1 (Q
C-2H@) @, (CHs) (CzHs)
Examples include CH81(0CHs)s.

Among these, preferable are branched hydrocarbon residues having 3 to 20 carbon atoms in which the carbon at the α position of %R is secondary or tertiary, especially those in which the carbon at the α position of % R is tertiary. It is a silicon compound having a branched hydrocarbon residue having 4 to 10 carbon atoms.

The contact conditions between the above-mentioned prepolymerized or non-prepolymerized solid catalyst component and the silicon compound represented by the above general formula are as follows:
Although any conditions may be used as long as the effects of the present invention are recognized, the following conditions are preferable for boat fishing. The contact temperature is −
The temperature is about 50 to 200°C, preferably 0 to 100°C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons,
Polysiloxanes (for example, the above-mentioned polymeric silicon compounds) and the like can be mentioned.

The amount of the silicon compound represented by the above-mentioned general formula may be arbitrary as long as the effects of the present invention are observed, but - for boat fishing, it is preferably within the following range. The atomic ratio of silicon (silicon/titanium) of the silicon compound represented by the above general formula to the titanium component constituting the solid component containing titanium, magnesium and halogen as essential components is within the range of 0.01 to 1000, preferably 0.1~10
It is within the range of 0.

(Liquid Hydrocarbon) As the liquid hydrocarbon used in the uninvented method, liquid hydrocarbons known for boat fishing are used. Specifically, n-pentane, impentane, n-hexane, n
- linear or branched aliphatic hydrocarbons such as hebutane, n-octane, isooctane, n-decane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane, benzene,
Aromatic hydrocarbons such as toluene and xylene, kerosene, and mixtures thereof can also be used.

(Polyolefin powder) As the polyolefin powder used in the present invention, any powder that can be recognized as having the effects of the present invention may be used.
- For boat fishing, polyethylene, polypropylene, polybutene, poly4-methylpentene, etc. are preferred, and copolymers of these with other olefins can also be used. The polyolefin used here is preferably one that has been sufficiently purified, and has an average particle size of 100
~1000 micron, more preferably 200-500 micron polyolefin powder.

Here, "sufficiently purified" polyolefin refers to a polyolefin powder that is substantially free of moisture, oxygen, other solvents, etc. on the surface and inside of the polyolefin powder.

The amount of liquid hydrocarbon and polyolefin powder to be used may be any amount as long as the effects of the present invention are recognized, but for boat fishing, it is preferably within the following range.

The amount of liquid hydrocarbon used is 1 per gram of catalyst component.
-1oo-dashi, preferably it, 2-2°-.

The amount of polyolefin powder used is preferably in the range of 0.01 to 10 grams, more preferably in the range of 0.1 to 1 gram, per 1 gram of the catalyst component.

(Drying method) In the method of the present invention, titanium obtained as described above,
An olefin polymerization catalyst component containing magnesium and halogen as essential components is suspended or mixed in a liquid hydrocarbon containing the polyolefin powder, and then dried.

This drying method can be any method known for boat fishing, and in most cases it is preferable to use a dryer. Types of dryers include material transfer type dryers, material transfer type dryers, material stirring type dryers, hot air transfer type dryers, cylindrical dryers, and the like. The operation can be carried out under reduced pressure and/or heating. For example, the pressure is 1 to 700 ■Hf, preferably 1O to 200 m
Hf, and the temperature is 0 to 100°C, preferably 10 to 8
It is 0°C.

The solid component thus obtained is combined with an organoaluminum compound exemplified below as a transition metal component of a Ziegler type catalyst, and used for olefin polymerization. here,
"Separate the fat content" means that it is prohibited to use the olefin polymerization catalyst component obtained by the method of the present invention in combination with other components, such as known electron donors, in addition to the organoaluminum compound. do not have.

(Organoaluminum compound) Specific examples of the organoaluminum compound used in combination with the catalyst component obtained by the method of the present invention include R
', -nAJ Xn or, R', -rnAJ (
OR' ) rn (where R4 and am are hydrocarbon residues or hydrogen atoms having about 1 to 20 carbon atoms, which may be the same or different, R6 is a hydrocarbon residue, X is a halogen, n and m
are respectively expressed as O≦n 3.0 (m (the number of a). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctyl Aluminum, trialkyl aluminum such as tridecyl aluminum, (b) alkyl aluminum halide such as diethyl aluminum monochloride, diimbutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) diethyl aluminum hydride, diisobutyl aluminum Examples include aluminum alkoxides such as hydride, (d)diethylaluminum ethoxide, and diethylaluminum phenoxide.

These organoaluminum compounds (a) to (c) may contain other organometallic compounds, such as R', , AJ(OR")a (where 1≦a≦3,
R'j? and R8 have 1 carbon number, which may be the same or different
~20 hydrocarbon residues. ) can also be used in combination with an alkyl aluminum alkoxide. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide,
Examples include a combination of ethylaluminum dichloride and ethylaluminum jetoxide, and a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride.

The amount of the organoaluminum compound to be used is in a weight ratio of organoaluminum compound/transition metal component of 0.1 to 1000, preferably 1 to 100.

(Use of Catalyst/Polymerization) The catalyst component obtained by the method of the present invention, the above-mentioned organoaluminum compound, and optionally a third component such as an electron-donating compound can be used as a catalyst for olefin polymerization. The catalyst is applied not only to ordinary slurry polymerization, but also to liquid-phase solventless polymerization, solution superposition, or gas-phase polymerization in which substantially no solvent is used. It is also applicable to continuous polymerization, batch polymerization or preliminary polymerization. As the polymerization solvent in the case of slurry polymerization, aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature ranges from room temperature to about 200°C, preferably from 50 to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time.

When slurry 17 + i is attached, the amount of catalyst component used is o,
A range of 0.0001 to 0.1 gram catalyst acid/liter solvent is preferred.

The olefins polymerized with the above catalyst system have the general formula R-C
H=CH, (where R is a hydrogen atom or a carbon number of 1 to 1
O is a hydrocarbon residue and may have a branched group. ). Specifically, ethylene, propylene, butene-1, pentene-11 hexene-1,4-
There are olefins such as methylpentene-1. Preferred are ethylene and propylene. In the case of these polymerizations, up to 50% by weight, based on ethylene, preferably up to 20% Fi20Mf, can be copolymerized with the above-mentioned olefins, and
Copolymerization with the above olefins, especially ethylene, at 0% by weight can be carried out. Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefins, etc.) can also be carried out.

Experimental Examples Example-1 [Synthesis of catalyst components] Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- introduce 200 ml of hebutane, then MtC
0.4 mol of I2, 'pi (Q-nC4Hg) 4
ko, 8 mol, etc., and reacted at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 48 milliliters of methylhydropolysiloxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane.

Next, the optically purified n was placed in a flask purged with nitrogen.
- Introduce 50 milliliters of hebutane and mix the solid component synthesized above with M? 0.24 mol was introduced in terms of atoms. Next, n-hebutane 25m IJ IJ TS) kK 5i (J
40.4-r=nil was mixed and introduced into a flask at 30°C for 30 minutes, and reacted at 70°C for 3 hours. After the reaction is complete,
Washed with n-heptane. Next, 0.024 mol of 7-taloyl chloride was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 70°C for 30 minutes, and then heated at 90°C.
The reaction was carried out for 1 hour.

After the reaction was completed, it was washed with n-hebutane. Then 5iC1
420 ml was introduced and reacted at 80°C for 6 hours. After the reaction was completed, it was washed with n-heptane. The titanium content of this was 1.21 weight percent.

Then internal volume 1.5 with stirring and temperature control device
In a small stainless steel stirring tank, 500 milliliters of optically dehydrated and deoxidized n-hebutane, 2.2 grams of triethylaluminum, and the solid component obtained above
-20 grams each were introduced. Temperature f in the stirring tank: 2
At 0°C, propylene was introduced at a constant rate and propylene polymerization was carried out for 30 minutes. After completion of IF, the sample was thoroughly washed with n-heptane. When a portion was taken out and the polymerization t of propylene was examined, it was found that the amount of prepolymerized propylene was 1.04 grams per gram of solid component.

Into a flask that had been purged with nitrogen, 7 tons of 50 milliliters of n-hemolyte prepared from N were introduced into the flask, and then 5 g of the prepolymerized component obtained above was introduced, followed by CH.

CH,Cf(.

The solution was then brought into contact at 30°C for 2 hours. After contact ends n-
Thoroughly washed with hebutane.

Then, t-0.6 grams of triethylaluminum was introduced, and the mixture was kept in contact for 2 hours at 30°C. After the contact was completed, it was thoroughly washed with n-hebutane. Then, CHl CHx CHs was contacted for 2 hours at 30°C. After the contact was completed, the catalyst component was thoroughly washed with n-heptane to obtain a catalyst component.

(Drying of Catalyst Component) A total of 4.5 grams of the catalyst component obtained above, 30 milliliters of n-hebutane, and sufficiently purified polypropylene powder (150-3
f: 4.5 g was introduced. 50
The temperature was raised to 0.degree. C., and the mixture was dried for 2 hours under continuous stirring (10 orpm) while flowing purified nitrogen gas.

As a result, the hebutane content of the dried catalyst component was 0.3
It was a heavy M4. Furthermore, the particle size distribution of the dried catalyst component was examined and was as shown in Table IA.

Polymerization of L-propylene] In a stainless steel autoclave with an internal volume of 1.51 J and equipped with a stirring and temperature control device, 2 milliliter of optically dehydrated and deoxidized n-heptane, 125 milligrams of triethylaluminum, and the components produced above were added. 15 milligrams of the components excluding the prepolymerized polymer and the polymer powder mixed during drying were introduced.

Next, 60 microliters of hydrogen was introduced, and the temperature and pressure were increased to a polymerization pressure of 5 kir/JG and a polymerization temperature of 75
Polymerization was carried out under the following conditions: °C and polymerization time = 2 hours. After polymerization,
The resulting polymer slurry was separated by t-filtration and the polymer was dried. As a result, 164.3 grams of polymer was obtained. -0.32 g of polymer was obtained from 10,000 filtrate, and boiling hebutane extraction test showed that all products 1.
1 (hereinafter abbreviated as T-1,I) is 99.0 weight percent, MFR=1.4 ylx.

Polymer bulk specific gravity = 0.48 f/CC% Polymer particle size distribution was as shown in Table-IB.

Comparative Example-1 The catalyst component was synthesized in exactly the same manner as in Example-1, and upon drying,
Drying was carried out in the same manner as in Example-1 except that no polymer powder was used. The particle size distribution of the catalyst components is shown in Table-IA.

Example-1 except that this dried catalyst component was used.
Polymerization of propylene was carried out in the same manner. As a result, 13
4.3 grams of polymer were obtained, T-1, I=98.
9 weight percent, MFR=1.9 f/10 min, polymer bulk specific gravity=0.46 t/J The polymer particle size distribution was as shown in Table 1B.

Examples 2 to 4 Catalyst components were synthesized in the same manner as in Example-1, except that during drying, the type of polymer powder used and t' were changed as shown in Table-2. It was dried in the same way. The results are shown in Table-2. Further, propylene polymerization was carried out in the same manner as in Example-1 except that the dried catalyst components obtained above were used. The results are shown in Table 3A and Table 3B.

(Space below) Example 5 (Manufacture of catalyst component) 75 ml of thoroughly degassed and purified n-hebutane was placed in a 1-liter flask that had been sufficiently purged with nitrogen, and anhydrous Mf (J2 (ball milled) was added to the flask. Ti (0-flc, ) I,) was ground for 24 hours.

110, milliliter, and 0.5 g of AlCll5 were introduced and reacted at 70°C for 30 minutes. Then n-
A mixture of 5.4 ml of butanol and 5.4 ml of n-hebutane was introduced through a spray nozzle in 95 seconds to form droplets of 140 microns, and reacted at 70°C for 1 hour. 2.3 ml of Ttcit4 was introduced therein, and the mixture was reacted at 70° C. for 1 hour. Next, 9 milliliters of methylhydrodiene polysiloxane was introduced and reacted at 70°C for 2 hours. After the reaction was completed, it was thoroughly washed with n-hebutane and used as a catalyst component.

(Drying) Add 5 grams of the above catalyst component to a flask purified in the same manner as in Example 1, add 50 milliliters of n-hex 71ft, and add 1 liter of polyethylene powder (300 to 500μ).
5 grams were introduced, heated to 55°C, and heated under a nitrogen atmosphere for 30 minutes.
Dry for an hour. As a result, the hexane content of the dried catalyst component was 0.21 weight percent.

Furthermore, when the particle size distribution of the dried catalyst component was examined, it was as shown in Table 4A.

(Polymerization of ethylene) In a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, the mixture was subjected to vacuum-ethylene displacement several times, and then thoroughly dehydrated and deoxidized.
- 800 milliliters of hebutane was introduced, followed by 100 milligrams of triethylaluminum, and t-5 milliliter of the catalyst component synthesized above. Introduced J-gram.

The temperature was raised to 85°C, water was introduced at a partial pressure of
It was set as plum/-G. Polymerization was carried out for 3 hours. These conditions were kept constant during the Jt meeting. However, as the pressure decreases as the polymerization progresses, the pressure is kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged, the contents were taken out from the autoclave, the polymer slurry was filtered through IJi, and the mixture was dried in a vacuum dryer overnight.

222 grams of polymer was obtained. This means that 44,400 grams of polymer (PE) were obtained per gram of solid catalyst component. [Catalyst yield (f-PE/f catalyst component) = 44,400]. When the melt flow rate (MFR)' of this polymer was measured, it was 4.39710.
It was a minute. The average particle size of the polymer is 941 microns.
The bulk specific gravity of the polymer was 0.36 f/CC. Furthermore, the particle size distribution of the obtained polymer was as shown in Table 4B.

Comparative Example-2 In Example-5, drying was carried out in the same manner as in Example-5 except that the siliconized ornament was not used during drying.

The particle size distribution of the catalyst components is shown in Table 4A. Polymerization of propylene was also carried out in the same manner as in Example 5, except that the dried catalyst component obtained above was used. As a result, 204 grams of polymer was obtained, MFR = 4.5f710 min, polymer average particle size = 968 microns, polymer bulk specific gravity = 0
．． It was 34f/CC.

The particle size distribution of the obtained polymer is shown in Table 4B.

(Margin below)

[Brief explanation of the drawing]

FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts. Patent applicant Mitsubishi Yuka Co., Ltd. agent Masahisa Hase Patent attorney agent Takaya Yamamoto Procedural amendment (method) December 1, 1988

Claims (1)

[Claims] (1) An olefin polymerization catalyst component containing titanium, magnesium, and halogen as essential components is suspended or mixed in a liquid hydrocarbon containing polyolefin powder with an average particle size within the range of 100 to 1000 microns. A method for drying a catalyst component for olefin polymerization, the method comprising: drying a catalyst component for olefin polymerization.