JPS6123603A - Olefin polymerization catalyst component - Google Patents

Abstract

PURPOSE:The titled catalyst component which has high activity and can give a polymer having a relatively large particle diameter and a controlled particle diameter distribution, obtained by contacting an alcohol compound and a liquid titanium halide compound with a thin surface layer of a specified particulate product of contact. CONSTITUTION:A product of contact is obtained by bringing 1mol of a Mg halide compound (e.g., MgCl2), 1X10<-3>-50mol of an alkoxy group-containing compound of a Group I -IV metal of the periodic table [e.g., Li(OC2H5)] and 1X10<-4>-1.0mol of an inorganic metal halide compound (e.g., LiCl) into contact with each other at -50-200 deg.C in the presence (absence) of a dispersion medium. The product is sprayed with 1X10<-4>-1mol of an alcohol compound (e.g., methanol) in the form of liquid drops of a 10-1,000mu diameter to form thin layers on the surfaces of the particles and then contacted with 1X10<-3>-50mol of a liquid titanium halide compound (e.g., TiCl4) at -50-200 deg.C to obtain an olefin polymerization catalyst component of an average particle diameter of 10-100mu.

Description

BACKGROUND OF THE INVENTION TECHNICAL FIELD The present invention relates to the transition metal component of five so-called Ziegler-type catalysts. According to the present invention, it is possible to obtain a catalyst component for olefin polymerization that is highly active and can propagate a polymer having a relatively large particle size.

It has been known that a highly active catalyst can be obtained by using a magne/ram compound such as magnenoum halide, magnenoum alkoxide, hydroquine magne7ium chloride, dialkylmagneneum, etc. as a carrier component.

By the way, when an olefin is polymerized using a Ziegler type catalyst using such a supported catalyst component (solid catalyst component), the resulting olefin polymer particles are obtained in the form of particles, but the particle size and particle size of the olefin polymer particles are The size distribution depends on the state of the particles of the solid catalyst component used. On the other hand, it is preferable that the produced olefin polymer particles have a relatively small particle size and have uniform particle sizes, as this leads to an improvement in the polymer concentration of the produced polymer slurry and to improved productivity due to easier handling of the polymer slurry. .

However, in the above-mentioned highly active catalysts, it is difficult to control the particle size of the catalyst components, and in many cases the average particle size is 5 to 1.
The particle size distribution of the catalyst is also wide and insufficient.

Therefore, it is currently desired to develop a method for producing a catalyst that has a relatively large average particle size of 10 microns or more and can control the particle size distribution.

Prior art Prior art includes JP-A-49-65999, JP-A-54-41985, JP-A-55-2951, JP-A-55-135102, JP-A-55-135103,
Examples include JP-A No. 56-67311 and various publications.

In these prior art techniques, the Mg compound as a carrier component is made into fine particles or melted, and then solidified by spray drying, granulation, or rapid cooling. In order to increase the catalyst particle size by these methods, as far as the present inventors know, a large amount of equipment investment is required, and there seems to be a problem that the distribution of the generated catalyst particles is wide.

SUMMARY OF THE INVENTION The present invention seeks to provide a solution to the above-mentioned problems and to rapidly accomplish this goal by means of a supported transition metal catalyst component made in a particular manner.

That is, the catalyst component for olefin polymerization according to the present invention is
A thin layer (d
(e) a liquid titanium halogen compound, the average particle size of which is in the range of 10 to 100 microns. It is.

Effects When olefin polymerization is carried out using the solid catalyst component according to the present invention as a transition metal catalyst component of a Ziegler catalyst,
It has high activity, relatively large particle size, and controlled particle size distribution. 1 remer is obtained.

The reason why the use of the catalyst component of the present invention makes it possible to obtain a polymer with high activity and controlled polymer particle properties as described above is not necessarily clear, but the combination of magnesium halogen compounds and metals from Groups 1 to 2 of the periodic table. It seems that one of the important requirements is to react the alcohol in a thin layer with the contact product of the paulownia alkoxy group-containing 11 compound and the inorganic metal halide compound.

The catalyst component of the present invention consists of a contact product of the following components.

(al Magnesium halide compound such as MgF
2, MgCl□, MgB r 2, MgI, , Mg(O
C2+-1,)CI, Mg(OC6H5)CI,
Mg(OCH3)CI.

There are Mg (OH) CI, etc.

(b) Compounds containing metal alkyne groups of Groups ■ to ■ of the periodic table, such as Li (OC2H5), Na (OC2H5),
Ca(OC2H5)2, zn(OC2H5)2, Mg(
OC2H5) 2, Mg(O1C3H7)2, B(OC
2H5)3, Al(OC2H5)3, Al(OiC3H
7) 3, S i (QC,,)I5) 4.5i(0-
nc4H0)4, Ti(OC2H15)4, Ti(O1
C3H7)4,TI(0-nC4T(,)4,Ti(
OC6H5)4,zy(OC2H3)4,Sn(OC
2H3) 4, Mg(QC2HJ)CI, 5i(OC
2H5)01%5i(OC2H5)2C1□, AI(O
C2H5)2C11Ti(OC4H8)3C1゜Ti(
OC2H5)2CI2, ■0 (0 mouth C4H3)3, T
i(OiC3T(7)lr2, etc.) Among these metal noalkoxy group-containing compounds, titanium alkoxy group-containing compounds and silicon alkoxy group-containing compounds are preferred, particularly tetraalcoquine titanium and tetraalcoquine titanium. Titanium is preferred.

(c3 Inorganic metal halide compound Any compound generally known as an inorganic metal halide compound can be used. Typical compounds include the following.

LiC1%NaCl, KCI%NaBr, BeC1
, CaCl2.5rCI BaCl ZrCl
MOCI3, Moc I 5.2%
21 4-CrCl MnCl F
eCl2, FeCl3, FeBr2.3%
2% FeBr COCl2, COBr2, N1cl□,
NiBr2, cucl CuC1, CuB r
ZnCl2, AlCl3.2%
2% A I B r A I I
B CI B B r Ge C12,G
e CI 4.3% 3-3%
3%S iCI S flCI Sn CI
P t CI 2, ptcx4. InCl3, W
Cl6, T I CI 3, T I CI 4° Among these inorganic halogen compounds, halogen compounds of metals in Groups 3 and 4 of the periodic table are preferred, particularly halogen compounds of aluminum, zirconium, and titanium. Suitable halogens are salts, odors and iodine.

(d) Alcohol Compounds One group of alcohol compounds to be used in the present invention are alkanols.

-hydric alcohols or polyhydric alcohols having about 1 to 20 carbon atoms, preferably 1 to 1 o, are generally suitable, and specifically, for example, methanol, ethanol, isopronominol, n-bronognol , inbutanol, n-butanol, hexanol, n-octatool, 2-ethylhexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoacetate, glycerin, and the like.

Another group of alcohol compounds to be used in the present invention are silanols. Silanols having about 1 carbon atom are generally suitable, and specifically, for example, trimethyl 7
Ranol, dimethyl 7ran.

Examples thereof include diol, diphenyl7landiol, phenylsilanetriol, and the like.

Another group of alcohol compounds to be used in the present invention is phenols such as phenol, orthocresol, and nocracresol.

(el Liquid titanium halogen compound) Here, "liquid" refers to not only those that are liquid themselves (including those that are complexed and become liquid), but also those that are liquid as a solution. include.

Typical compounds include the general formula Ti(OR)4-nX
n (here, R is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, and n
indicates a number of 0 < n < 4. ) can be mentioned.

Specific examples include TiCl4, T t B r 4, Ti
(OC2H5) CI3, TI (OC2H5) 2”2, T
i (OC2H5)3C1゜Ti(OiC3H7)C1
3, Ti(OnC4H9) CI3, Ti(OnC4H9
)2C1,,Ti(OC2H5)Br3°Tl(OC2
H5) (OC4H9) C12, TI (onc4u,)
3Cl.

Ti(0-C6H5)C13, Ti(QC5H,)C
13, Ti(OC6H13)C13, and the like.

The liquid titanium halogen compound to be used in the present invention may be a molecular compound obtained by reacting the aforementioned titanium halogen compound with an electron donor. Specific examples of such metal compounds include TiCl4・CH3COC2H5, T I CI 4
・CH3CO2C2H5, TiCl4@C6H5NO3
, TiC14-CI (, COCl, TlCl4・C6H
5COCl, T sc I 4・C6H5CO2C2
H5, equal force t can be raised.

Further, the following polymeric silicon compound (fl) can be used in combination with the liquid titanium halogen compound.

That is, this is a polymer silicon compound having a structure represented by -8i-0- (R is a hydrocarbon residue, and the number of carbon atoms is about 1 to 10), and specific examples include , methylhydroborinoxane, ethylhydropolinoloxane, phenylhydropolysiloxane, noclohexolhydroporinoxane, and the like.

The degree of polymerization of these polymeric silicon compounds is not particularly limited, but in consideration of handling in the throat, it is preferably about 10 centistokes to 100 centistokes.

Although the terminal structure of these hydroboriaoxanes does not have a large effect on the catalyst component of the present invention, it is preferable that the terminal structure is capped with an inert group such as a trialkyl 7-lyl group. Among these polymeric silicon compounds, alkylhydronoloxanes, especially methylhydronoloxanes, are preferred.

Preparation of the Catalyst Component The catalyst component according to the invention is prepared by contacting the components described above in a specific order or manner.

Amount ratio The amount of each component to be used is as long as the effect of the present invention is recognized.
Although it can be arbitrary, it is generally preferably within the following range.

The amount of the alfquinodo compound of group gr to group metal of the periodic table to be used may be in the range of 1 x 10 to (2) in molar ratio to the halogen compound of red sea bream and gnome, and more preferably in the range of 1 to 10. It is within.

The amount of inorganic metal halogen compound used is 1 x 10 to 1.0 in molar ratio to the amount of magnesium halogen compound used.
It may be within the range of, more preferably 1×1O−3 to 1
It is within the range of X40-'.

The amount of alcohol to be used may be in a molar ratio of 1 x 10 to 1, more preferably 0.1 to 0.8, relative to the halogen compound of magnesium.

The amount of the liquid titanium halogen compound to be used is 1X10-" to 1X10-" in molar ratio to the magnesium halogen compound.
It may be within the range of 50. When used in combination with a polymer silicon compound, it is preferably within the range of 5 x 10 to 4 x 10. The amount of the polymeric silicon compound to be used may be in the range of 1X10-' to 5000, more preferably in the range of 1X10'' to 560, in terms of molar ratio to the magnesium halogen compound.

Contacting each component The contacting of each component is limited to the extent that the contacting of the alcohol compound is carried out in a specific manner. It may be of any kind as long as the effect of the invention is recognized. The contact temperature is -50℃
The contact may be made within the range of ~200°C.

The contact between the magnesium halogen compound (al) and the alkoxide compound of a metal from group III of the periodic table (bl) and the inorganic metal halogen compound (c) involves the simultaneous application of the latter two compounds to the particle surface of the magnesium halogen compound (c). Alternatively, by contacting in stages, specifically, magnesium halogen compound particles can be brought into a liquid state (a solution may also be used).
This is done by stirring the two compounds or their solutions together. Mechanical pulverization using a ball mill, vibration mill, etc. can also make the contact between the components more complete.

Each component should be brought into contact in the presence of a dispersion medium.
'1 can also be done. In that case, the dispersion medium includes hydrocarbons, halogenated hydrocarbons, dialkyl poly/a-xane,
etc. Specific examples of hydrocarbons include hexane, heptane, toluene, nochlorohexane, etc. Specific examples of halogenated hydrocarbons include n-butyl chloride, 1.2 dichloroethylene, carbon tetrachloride, chlorobenzene, etc. , Specific examples of dialkylpolineloxane include dimethylpolineloxane, methyl-phenylpolysiloxane, and the like.

Magnesium halogen compounds (Al and periodic table No.
The contact product between the alkokyno group-containing compound (bl and the inorganic metal halogen compound (c) of the group II metal and (d) alcohol is the reaction between the magnesium halogen compound fal and the alkoxyd compound (bl and the inorganic metal halogen compound (c)). Compound(
The alcohol compound contacts only the surface portion of the contact product with c) and is carried out in such a way that it becomes unsightly. Therefore, the method of immersing (al-(c) contact product particles) in an alcohol compound bath is not preferred unless the immersion is short and the alcohol compound rdl does not penetrate to the center of the particles.

A preferred method (V) consists of attaching 10 to 1000 ml of alcohol to the surface of the particles.

At this time, the alcohol or alcohol diluted solution is
Situations such as immersing the particles in excess alcohol solution are preferably avoided. The contact time is preferably relatively short, and the contact time may be about 1 second to 5 minutes.

The solid particles obtained as described above are brought into contact with the liquid titanium halogen compound (e) (and optionally the polymeric silicon compound (f)), and the compound (a) and the compound (
This can be done as described above for contact with bl and (cl).

Formation of Olefin Polymerization Catalysts The catalyst components of the present invention can be used in the polymerization of olefins in combination with an organometallic compound as a cocatalyst.

Any of the organometallic compounds of metals in groups 1 to 2 of the periodicity table, which are known as cocatalysts, can be used.

Particularly preferred are organic aluminum compounds. Specific examples of organoaluminum compounds include the general formula % (R, R, R are hydrocarbon residues or hydrogen having 1 or more carbon atoms, which may be the same or different, X is a halogen, n and m
are the numbers of O x 2.0 x 1, respectively. ). Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisoditylaluminum, triakylaluminum, trioctylaluminum, tritenrualuminum, etc.; 1) diethyl-aluminum monochloride, noisozotylaluminum; Alkyl aluminum halides such as monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) dialkyl aluminum hydride such as diethyl aluminum hydride, diisobutylaluminium rhamno hydride, and (c) diethylaluminium ethoxide, diethylaluminium hydroxide. Examples include alkylaluminum alkoxides such as diethylaluminum phenoxide, diethylaluminum phenoxide, and the like.

These (a) to (c) organoaluminum compounds may contain other organometallic compounds, such as R;-aAl(OR8)a(1
<3, R7 and R8 are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different. ) can also be used in combination with an alkyl aluminum alcokind represented by: For example, a combination of triethylaluminum and diethylaluminum ethoxyd, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminum ethoxyd, and diethylaluminum chloride, etc. Can be used in combination with

The amount of these organometallic compounds to be used is not particularly limited, but the weight ratio is 0.5 to 1 with respect to the solid catalyst component of the present invention.
It is preferably within the range of 000.

In order to improve the stereoregularity of an olefin polymer having 3 or more carbon atoms, it is effective to add and coexist an electron-donating compound such as an ether, ester, or amine during polymerization. The amount of the electron-donating compound used for this purpose is 0.001 to 2 mol, preferably 0.01 to 1 mol, per 1 mol of the organoaluminum compound.

Olefin The olefin polymerized with the catalyst system of the present invention has the general formula R-C
H=CH2 (where R is a hydrogen atom, or has 1 to 1 carbon atoms)
0 hydrocarbon residue, which may have a branching group).

Specifically, there are olefins such as ethylene, propylene, zothene-1, pentene-1, and hexene-1,4-methylpentene-1. Preferred are ethylene/and propylene. In these polymerizations, it is possible to carry out copolymerizations with up to one percent by weight of the above olefins, preferably 20 percent by weight, relative to ethylene, and 30 percent by weight relative to propylene. It is possible to carry out copolymerization with the above olefins, especially with ethylene. Copolymerization with other copolymerizable monomers (eg vinyl acetate, diolefins) can also be carried out.

Polymerization The catalyst system of the present invention is applicable not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization in which substantially no solvent is used. It is also applicable to continuous polymerization, batch polymerization, or prepolymerization methods.

In the case of slurry polymerization, the polymerization solvent used is saturated aliphatic such as hexane, heptane, pentane, nclohexane, benzene, toluene, etc. or aromatic raw carbon (hydrogen) alone or in mixtures.The polymerization temperature is from room temperature to 200°C.
temperature, preferably 500C to 150C, and hydrogen can be used as an auxiliary molecular weight regulator at that time.

Experimental Examples Example-1 75 milliliters of thoroughly air-purified n-hebutane was placed in a 1-liter flask that had been sufficiently purged with nitrogen, and anhydrous Mgc 12 (a) (pulverized in a ball mill for 24 hours) was added. ), 10 grams of Ti (0-nC4)
I9) 10 ml of 4(b) and AICl
(0.5 g of Cl was introduced and reacted at 70°C for an addition period.Next, a mixture of 15.4 ml of n-citanol (d) and 5.4 ml of n-hebutane was added to form droplets of 140 microns. was introduced from a spray nozzle for 5 seconds and reacted at 70°C for 1 hour.
2.3 milliliters of l4(el) was introduced and the reaction was carried out at 70°C for 1 hour.

Next, 9 milliliters of methyl hydrogenoboria xane (fl) was introduced and reacted at 70°C for 2 hours → t. After the reaction was completed, the Tr content in the M# component was measured and found to be 9.8 fold ffax'. The average particle size of the catalyst components was measured by a sedimentation method and was found to be 26 cents.
．． It was 3 microns.

Polymerization of ethylene Into a stainless steel autoclave with an internal volume of 1.5 liters equipped with stirring and temperature control equipment, after repeating vacuum-ethylene displacement several times, 800 ml of hebutane, which had been thoroughly dehydrated and taxed, was introduced. Then, 100 milligrams of triethylaluminum and 5 milligrams of the catalyst component synthesized above were introduced.

The temperature was raised to 85°C, hydrogen was introduced at a partial pressure of 4 to 2, and ethylene was introduced to 5 KP/crn2, and the total pressure was 9 K97.
It was set as C112G. Polymerization was carried out for 3 hours. These conditions were kept constant during the polymerization. However, the pressure, which decreased as the polymerization progressed, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were injected into the autoclave, and the contents were taken out from the autoclave. The polymer slurry was filtered and dried in a vacuum dryer overnight. A polymer of 232 durams was obtained. This means that 46,400 grams of polymer (PE) were obtained per gram of solid catalyst component. [Catalyst yield (9・PE19% medium component) = 46.40011゜ Melt flow rate of this polymer (MF
R) was measured and found to be 4.1 (9/10 minutes). The average particle size of the polymer is 941 microns;
The bulk specific gravity was o, aa (9/cc).

Example 2 Production of catalyst component In the production of the catalyst component in Example 1, 3.4 milliliters of ethanol (d) was used instead of n-butanol (d), and the amount of TIC14 (el) used was Make 5ml and add methylhydrogenfuroxane rf)
The catalyst component was produced in exactly the same manner except that the catalyst component was not used. The Ti content was 4 microns.

Polymerization of ethylene Ethylene was polymerized under the same conditions as in Example 1. 143 grams of polymer was obtained [yield vs. catalyst (
g-PE/l catalyst component) = 28,600).

Polymer average particle size = 860 microns, polymer bulk specific gravity =
0.33 (9/cc).

Example-3 Production of catalyst component In the production of the catalyst component of Example-1, Ti(0-nC4Hg)4 (b171'wari5i(O
The catalyst component was produced in exactly the same manner except that Et)4(bl was used and 41 ml of TiCl5(clO) was used in place of AlCl5(c).The Ti content was 7.2% by weight. Yes, the average particle size is 1
It was 9.5 microns.

Ethylene Polymerization Ethylene polymerization was carried out in exactly the same manner as in Example 1 except that 200 mg of triinobutylaluminum was used instead of triethylaluminum.

103 grams of polymer was obtained (yield based on catalyst (9 pots PE/9·catalyst component) = 20.600). MFR
=5.3 (9/10 minutes), polymer average particle size = 485
Micron, polymer bulk specific gravity = 0.32 (9/cc)
Met.

Example-4 Production of catalyst component In the production of catalyst component of Example-1, AlCl5(c
) The catalyst component was prepared in exactly the same manner except that 88 grams of Z r C14 (cIO-88) was used instead of Z r C14 (cIO-88 grams).

The Ti content was 10.6 wt. e-cents and the average particle size was 23.6 microns.

Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Example-1.

208 grams of polymer was obtained [with respect to catalyst absorption (9.
287g/catalyst component) = 41,600).

MFR = 4.3 (9/10 minutes), polymer average particle size = 831 microns.

Example-5 Polymerization of mixed gas of ethylene and butene-1 In the polymerization of Example-1, an ethylene-butene-1 mixed gas containing 10 volume percent of butene-1 was used instead of ethylene, and the polymerization temperature was changed. Polymerization was carried out in exactly the same manner except that the temperature was 65°C.

227 grams of polymer was obtained [versus catalyst yield (9.
PE19/catalyst component) = 45.400]. MFR
=3.6 (9/10 minutes), polymer average particle size = 925
micron, and high specific gravity = 0.32 (9/cc).

Further, the polymer density was 0.934 (9/cc).

Applicant's agent Kiyoshi Inomata 1 Indication of the case 1982 Patent application No. 143306 2 Name of the invention Catalyst component for olefin polymerization 3 Relationship to the person making the amendment Case Patent applicant (605) Mitsubishi Yuka Co., Ltd. 4th generation Manager 8 Amend the statement of contents of the amendment as follows.

[1) Page 2, line 13 Correct "small particle size" to 1 large particle size.

(2) Page 12, lines 13-14 1. Delete "or its solution".

(3) Page 14, line 2 Add the following sentence after "product particles":

"or a suspension of said particles under IS stirring" (4) Same page, 3rd line Correct "adhesion" to "contact".

(5) In lines 6 and 7 of the same page, "as an amount that can cause wetting" is amended to "as an amount that can cause wetting."

(6) Page 19, line 10 Add the following sentence next to "It caused a reaction."

"The obtained particles had a structure in which small particles were aggregated and bonded before the addition of butanol." (7) Page 21, line 10, "The Ti content was 28 microns." .7% by weight, and the average particle size was 28 microns.''

(8) Add the following sentence between page 23, lines 17 and 18.

"Example 6 Arashi If a [ζゑSufficiently purified polyethylene powder was charged into the apparatus, and then 100 milligrams of triethylaluminum and 10 milligrams of the solid component synthesized in Example-1 were introduced. Next, 0.7 milligrams of H2 was introduced.
Kg/ctA was introduced, the temperature was raised to 85°C, the introduction of an ethylene-butene-1 mixed gas containing 12 volume percent butene-1 was started, and the total pressure was increased to 9'j/cm, and polymerization was carried out at 85°C for 2.5 hours. Ta. 301 grams of polymer were obtained.

MFR=1.6 (g/10 min), polymer density -〇,
924 (shi/ctd).

Moreover, the average particle diameter of the polymer was -831 microns. ”

Claims (1)

[Claims] (d) An alcohol compound is added to a thin layer on the particle surface of the contact product of (a) a magnesium halogen compound, (b) an alkoxy group-containing compound of a group I to IV metal of the periodic table, and (c) an inorganic metal halogen compound. and (e) a liquid titanium halogen compound, the catalyst component for olefin polymerization being characterized in that the average particle size is within the range of 10 microns to 100 microns.