JPH0374412A - Production of polyolefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polyolefin having excellent bulk specific gravity, powder properties, etc., even with a small amount of aluminoxane used by polymerizing an olefin by the use of a solid catalytic component prepared by supporting a specific transition metal compound and a aluminoxane on inorganic particulate carrier. CONSTITUTION:(A) A transition metal compound [e.g. dimethylsilylbis (methylcyclopentadienyl)zirconium dichloride] shown by the formula (R1 is H, silyl, etc.; X is H, halogen, etc.; Y is silicon or germanium; n and q are 0-4) and/or (B) an aluminoxane is supported on (C) an inorganic particulate carrier (preferably particles of SiO2 having 10-100mum diameter) to give a solid catalytic component (preferably in the ratio of 0.05-200 millimol transition metal atom of the component A and 50-10,000 millimol aluminum atom of the compo nent B based on 100g component C) and an olefin is polymerized by using the solid catalytic component.

Description

[Detailed description of the invention]

[Field of application in the fa industry] The present invention relates to a method for producing an olefin polymer. More specifically, by supporting the catalyst component on an inorganic carrier, it is possible to polymerize olefins with excellent polymerization activity even when the amount of aluminoxane used is reduced, and the olefin polymer has a large bulk specific gravity and excellent powder properties. A method of manufacturing a coalesce is discussed. [Prior Art and its Problems] As a homogeneous catalyst for olefin polymerization, the so-called Kaminsky catalyst is well known. This catalyst has a very high polymerization activity, and is known to be capable of producing atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene, for example, in propylene polymerization. (M
akro kou o1゜Cham, Rapld Cosmun
, 4, 417-421 (11a3), ^ngewChe
Sono, Int, Ed, Engl, 24, 507-508 (
1985), J, ^m, (t+em. Soc, 1987.109.6544-8545.J,
^-, Cham, Soc, 1988°110.6255
-62581 However, the bulk specific gravity of the polymers obtained from these homogeneous catalysts was small, and it was difficult to obtain polymers with excellent powder properties. On the other hand, attempts have also been made to polymerize olefins using catalysts in which either one or both of a transition metal compound and aluminoxane are supported on a particulate carrier. For example, methods for carrying particulate polymers include JP-A-63-112.821 and JP-A-63-260.
．． Publication No. 903 can be mentioned. In addition, as a method using an Mg compound as a carrier, JP-A No. 6
2-230,802, JP-A-63-168,408, JP-A-83-168.409, JP-A-63-175,0
04, JP-A-64-6.003, JP-A-84-6.00
4, JP-A-1984-6,005, JP-A-64-11゜10
4. Japanese Unexamined Patent Publications No. 11, 105, 1984, etc. have been proposed. Furthermore, methods for carrying out polymerization by supporting a catalyst on an inorganic oxide carrier such as silica, silica-alumina, or alumina include JP-A-61-108,610;
27[1,+105, Japanese Patent Publication No. 11-298,008,
JP-A-63-22゜804, JP-A-63-2110.7
03, Japanese Patent Publication No. 63-51407. Japanese Unexamined Patent Publication No. 113-54,
403, Japanese Patent Application Publication No. 1983- Ill, 010, Japanese Patent Application Publication No. 1983-
68,206, JP-A-83-89.505, JP-A-83-89
-152,608, JP-A No. 63-213.504, and JP-A No. 63-248,803 have been proposed. However, even if olefins are polymerized using a solid catalyst component supported on a certain inorganic carrier in prior art C, the polymerization activity is low, and the powder properties such as the bulk specific gravity of the raw tL1 aggregate are There was a problem that only sufficient results could be obtained. As a result of repeated research to solve the above-mentioned problems, the present inventors have found that by using a transition metal compound [81, which will be described later] as the second transition metal compound component, the polymerization activity is high, the bulk specific gravity is large, and the powder properties are improved. It has been discovered that an excellent polymer can be obtained, and the present invention has been achieved based on this finding. [Means for Solving the Problems] That is, the present invention provides a transition metal compound represented by [B]-formula [11] (however,
M is a transition metal of titanium, zirconium or hafnium, Y is silicon or germanium * R'1C
1) 14-11 and R'q-(:5H4-* represent an unsubstituted or substituted cyclopentadienyl group, n and q are integers from O to 4, but 5 and 5 do not simultaneously take a value of 0, Each R1 may be the same or different from each other and represents hydrogen, a silyl group, or a hydrocarbon group, but the position and type of R1 on the cyclopentagenyl ring shall be such that no plane of symmetry including 5M exists. . Each R2 may be the same or different from each other and represents hydrogen or a hydrocarbon group, and X may be the same or different and represents hydrogen, halogen or a hydrocarbon group), [C] Al main In the catalyst formed mainly from xane, either [B] or [C] (
1) [^] Inorganic particulate carrier, one or the other, or [B], [C] both acid components,

[A] &:
This invention relates to a method for producing an olefin polymer characterized by polymerizing an olefin using a supported solid catalyst component. The solid catalyst component [A
] is an inorganic particulate carrier. Specifically, sio...
^1303, MgOlZr0m TiJ,! hos,C
These inorganic particulate carriers, which may be a0% ZnO, etc., or a mixture thereof, usually have a molecular weight of 100~! ,000
C., preferably 200 to 0.degree. C. before use. The carrier has its fl! ! Although the properties vary depending on the manufacturing method, the particle size is 5 to 200 μm, preferably 10 to 100 μm.
A material in the μm range is used. Further, these carriers may be subjected to preliminary contact treatment with an organoaluminum compound or a halogen-containing silane compound before supporting the transition metal compound or altoranoxane. Solid catalyst component [B
] is a transition metal compound having a bis-substituted cyclopentagenyl bridge type bidentate ligand with a bridge structure. - In formula [1], M is a transition metal such as titanium, zirconium or hafnium, preferably zirconium. Y is silicon or germanium. 2
The number of substituents on each cyclopentadienyl ring may be any number from unsubstituted to 4-position tII*, but at least one of the cyclopentadienyl rings should have a substituent. Each R1 may be the same or different and represents hydrogen, a silyl group, or a hydrocarbon group (alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having 1 to 20 carbon atoms); The position and type on the cyclopentadienyl ring shall be such that there is no plane of symmetry containing M. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, trifxnylsilyl group, etc. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, tert-butyl group, phenyl group, tolyl group, biphenyl group, naphthyl group, etc. Yes, each R2
may be the same or different and are hydrogen or the above-mentioned hydrocarbon groups. Also, X is hydrogen or fluorine,
These are halogens such as chlorine, bromine, and iodine, or the above hydrocarbon groups. Non-limiting examples of the above transition metal compounds include dimethylsilylbis(methylcyclopentagenyl)zirconium dichloride, dimethylsilylbis(t-butylcyclopentagenyl)zirconium dichloride, dimethylsilyl(cyclopentagenyl)(methyl cyclopentagenyl) zirconium dichloride, dimethylsilyl (cyclopentagenyl) (1-butylcyclopentagenyl) zirconium dichloride, dimethylsilyl (methylcyclopentagenyl) (t-butylcyclopentagenyl) zirconium dichloride, dimethyl Gel main rubis (methylcyclopentagenyl) zirconium dichloride, dimethylsilyl (methylcyclopentagenyl)
(2,4-dimethylcyclopentagenyl) zirconium dichloride, dimethylsilylbis(2,4-dimethylcyclopentagenyl) zirconium dichloride,
Zirconium compounds such as dimethylsilylbis(2,3,5-trimethylcyclopentagenyl)zirconium dichloride, dimethyl gel-based rubis(2,4-dimethylcyclopentagenyl)zirconium dichloride, dimethylsilylbis(methylcyclopentagenyl) ) titanium dichloride, dimethylsilylbis(2,4-dimethylcyclopentagenyl)titanium dichloride, dimethylsilylbis(2,3,5-trimethylcyclopentagenyl5-titanium dichloride, etc.),
dimethylsilylbis(methylcyclopentagenyl) hafnium dichloride, dimethylsilylbis(2,4-dimethylcyclopentagenyl) hafnium dichloride,
Hafnium compounds such as dimethylsilylbis(2,3,5-)-dimethylcyclopentadienyl)hafnium dichloride can be mentioned. Solid catalyst component [C
I is - formula

[■], or - formula [ml, R”OAI
(OAI) m-0AIR'z = [
It is an organoaluminum compound represented by If ]3s. R@ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and preferably a methyl group or an ethyl group. m is 4
~BO is an integer, preferably 6 or more. Methods for producing this type of compound are known, and include, for example, a suspension of a compound containing adsorbed water, a salt II containing water of crystallization (sulfuric acid hydrate, aluminum sulfate hydrate, etc.) in a hydrocarbon medium. An example of the method is to add trialkylaluminium to the reactor. In the present invention, the following method can be adopted as a method for supplying aluminoxane [CI] to the polymerization reaction system. (2) A method in which only the transition metal compound [B] is supported on an inorganic particulate carrier [^], and the solid catalyst component and al[noxane [C1] are respectively supplied to the polymerization reaction system. (2) As the solid catalyst component, an inorganic substance A method in which only aluminoxane [CI is supported on a particulate carrier [A], and the solid catalyst component and the transition metal compound [81] are respectively supplied to the polymerization reaction system. (3) An inorganic particulate carrier is used as the solid catalyst.

[A] transition metal compound

[B] A method in which both of Al9noxane [CI] are supported and the solid catalyst component is supplied to the polymerization reaction system. (4) The solid catalyst component of (2) above is used as the solid catalyst component, and the solid catalyst component and the transition metal compound [B]
A method of supplying al-1-noxane [CI] to a polymerization reaction system. (5) Solid catalyst component: Using the solid catalyst component of (3) above, aluminoxane [C1
A method of supplying to a polymerization reaction system. In the present invention, inorganic particulate carrier [A] L transition metal compound

As methods for supporting 0, the following (a) to (C
) method can be adopted. (a) A method of forming a solid catalyst component by bringing a solution of a transition metal compound into contact with an inorganic particulate carrier. (b) A method of forming a solid catalyst component by contacting a suspension of an inorganic particulate carrier dispersed in a solution of a transition metal compound with a solvent in which the transition metal compound is insoluble or poorly soluble. (c) A method of forming a solid catalyst component by distilling off the solvent from a suspension of an inorganic particulate carrier dispersed in a solution of a transition metal compound. In addition, aluminoxane [C1
The following methods (d) and (@) can be used as a method for supporting the . (d) A method of forming a solid catalyst component by contacting a suspension of an inorganic particulate carrier dispersed in a solution of aluminoxane with a solvent in which aluminoxane is insoluble or poorly soluble. (@) A method in which a solid catalyst component is formed by dispersing it in an aluminoxane solution and distilling off the solvent from a suspension of an inorganic particulate carrier. In addition, inorganic particulate carrier

[^] transition metal compound [81
% aluminoxane [C1], the following methods (f) to 0) can be used. (f) A suspension of inorganic particulate carriers dispersed in a solution of aluminoxane is brought into contact with an insoluble or poorly soluble solvent for aluminoxane to form an altoranoxane-supported carrier, and then the supported carrier and a transition metal are formed. A method of forming a solid catalyst component by contacting a solution of a compound or by distilling off a solvent from a suspension of the carrier dispersed in a solution of a transition metal compound. (g) After dispersing in a solution of aluminoxane and distilling off the solvent from a suspension of an inorganic particulate carrier to form an aluminoxane-supported carrier, the supported carrier is brought into contact with a solution of a transition metal compound. Alternatively, a method of forming a solid catalyst component by distilling off the solvent from a suspension of a support carrier dispersed in a solution of a transition metal compound. (h) After the transition metal compound-supported carrier is formed into an IL-like structure by contacting the transition metal compound solution with the inorganic particulate carrier, the aluminoxane is insoluble or difficult to dissolve in a suspension in which the supported carrier is dispersed in the center of the aluminoxane solution. A method of forming a solid catalyst component by contacting it with a soluble solvent or by dispersing it in a solution of aluminoxane and distilling off the solvent from a suspension of the supported carrier. (1) A transition metal compound supported carrier is formed by distilling off the solvent from a suspension of an inorganic particulate carrier dispersed in a solution of a transition metal compound, and then the supported carrier is dispersed in an aluminoxane solution. A method of forming a solid catalyst component by bringing the resulting suspension into contact with a solvent in which aluminoxane is insoluble or sparingly soluble, or by distilling off the solvent from a suspension of the carrier in which aluminoxane is dispersed in the center of the solution. Examples of solvents in which the transition metal compound [81] can be soluble include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, and halogen-containing hydrocarbons such as chlorobenzene and dichloroethane. Examples of insoluble to II-soluble solvents for the transition metal compound [B] include aliphatic or alicyclic hydrocarbons such as pentane, hexane, decane, dodecane, and cyclohexane. Examples of solvents in which aluminoxane (CI) is soluble include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. Examples of insoluble or sparingly soluble solvents for aluminoxane (CI) include aliphatic or alicyclic hydrocarbons such as pentane, hexane, decane, dodecane, and cyclohexane. When the solid catalyst component prepared by the above method contains a transition metal compound [81] per 100 g of inorganic particulate carrier,
The transition metal atom concentration is 0.01 to SOO mmol, preferably O,OS to 2001 mmol. *Ta,
Aluminoxane [when containing CI, the aluminum atomic concentration is 1 to so, ooo1t, preferably 5
Contains 0 to 10.0 OOJ remol. Furthermore, C1 transition metal compound [81 and aluminoxane [C
When both I are contained, the content is also within the above range, but the atomic ratio of aluminum to transition metal (^
1/M) is 1 to 2000. Preferably it is in the range of 5 to 1500. In the method of the present invention, the olefins used in the polymerization reaction are ethylene, propylene, l-butene, 4-methyl-! - α-olefins such as pentene, l-hexene, 1-octene, 1-decene, 1-dodecene, l-tetradecene, l-hexadecene, l-octadecene, 1-eicosene, etc., and a mixture component of two or more of these can also be subjected to polymerization. The above α-olefins, butadiene, 1.4-hexadiene, 1.4-pentadiene, 1.
7-octadiene, 1. Thononasien,! , conjugated and non-conjugated dienes such as dodecadiene, etc., or styrene, or cyclic olefins such as cyclopropane, cyclobutene, cyclohexene, norbornene, dicyclopentadiene, etc. The polymerization method used in the method of the present invention can be either liquid phase polymerization or gas phase polymerization. In the liquid phase polymerization, an inert hydrocarbon may be used as a solvent, and it is also possible to use a liquefied olefin itself such as liquefied propylene or liquefied butene-1 as a solvent. Examples of polymerization solvents include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, butane, isobutane, pentane, hexane, octane, decane, dodecane,
Aliphatic hydrocarbons such as hexadecane and octadecane, cyclopentane, methylcyclopentane, cyclohexane,
Alicyclic hydrocarbons such as cyclooctane, gasoline, kerosene,
Examples include petroleum fractions such as light oil and the like. The concentration of transition metal atoms in the polymerization reaction system in the method of the present invention is not particularly limited, but is preferably in the range of 10-'' to 10-101 ojl/41 in terms of transition metal atom concentration. There is no particular limit to the amount, but the molar ratio of ^l/transition metal atom is 10 or more, preferably 20 or more. The olefin pressure in the polymerization reaction system is not particularly limited, but is preferably normal pressure to 50 kg. /cm"G, and the polymerization temperature is also not particularly limited, but is usually in the range of -50 to 23Q°C, preferably -100°C. Molecular weight adjustment during polymerization can be carried out by known means, such as temperature selection. Alternatively, it can be carried out by introducing hydrogen. In the method of the present invention, it is preferable to prepolymerize the olefin in the presence of a solid catalyst component containing a transition metal compound prior to the polymerization of the olefin.
0.01 to 1003 per gram of solid catalyst, preferably 0
．． It is carried out by polymerizing 1 to 60 g of olefin. The olefins used for prepolymerization include ethylene, propylene, l-butene, 4-methyl-1-pentene, 1-hexene, l-octene, l-decene, 1-
Examples include dodecene and 1-tetradecene. [Effects of the Invention] According to the present invention, it is possible to produce an olefin polymer that has a high bulk specific gravity and excellent powder properties, without decreasing its polymerization activity even if the amount of alumoxane used is reduced.

【Example】

Next, the present invention will be specifically explained using examples. Example 1

[Preparation of solid catalyst component]

In a 300 sjl glass reaction vessel, silica calcined at aOO℃ for 12 hours (Fuji Davison Chemical #952) was placed in a 300 sjl glass reaction vessel.
12g and 2G tglL of toluene were added to form a suspension. In addition, 1 containing Tosoh Axie's methylaluminoxane (molecular weight 990) equivalent to 5 mmol of ^lH.
OO12 toluene solution was added. After stirring at room temperature for 30 minutes, nitrogen was flushed for 1 hour and toluene was distilled off, and o, os
50 containing qlmol of dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride
m dish of toluene solution was added. After stirring at room temperature for 30 minutes, nitrogen was flushed for 2 hours and toluene was distilled off to prepare a solid catalyst component. [Prepolymerization] In a 300s11 glass reaction vessel, 50% of polymerization was carried out under a nitrogen atmosphere.
After adding purified toluene at 1° C. and the entire amount of the above solid catalyst component, propylene was passed through the mixture at room temperature for 3 hours. After propylene was passed through the system, the inside of the system was replaced with nitrogen, and nitrogen was further passed at room temperature for 10 hours to distill toluene off. Example 2 [Polymerization] In a gas-phase autoclave made of SUS with an internal volume IL that was sufficiently purged with nitrogen, 5f1g of polypropylene powder (manufactured by Chisso Petrochemical Co., Ltd.) and methyl (manufactured by Tosoh Akzo ■) corresponding to 101 mol of ^l atoms were added. Aminoxane (molecular weight 9
After adding 2 G+l of a toluene solution containing 90), nitrogen was flowed for 1 hour and toluene was distilled off. Then, the entire amount of the prepolymerized solid catalyst component prepared in Example 1 was added. Total pressure is 10Kg/ with propylene
cm"G, and polymerization was carried out at 50°C for 2 hours. After completion of the polymerization, the total yield of the obtained polymer was 130 g.
and the catalytic activity was 8.6 g/gZr-hr. The apparent bulk specific gravity was 0.44 g/mA. Example 3

【polymerization】

In a 5115 gas-phase autoclave with an internal volume of IL that was sufficiently purged with nitrogen, 30 g of polypropylene powder (manufactured by Chisso Petrochemical Co., Ltd.) and methylaminoxane (molecular weight @
Example 1
After adding the entire amount of the prepolymerized solid catalyst component prepared in above, the total pressure was adjusted to 10 Kg/c+*''G using ethylene, and polymerization was carried out at 50°C for 1.5 hours. The total yield of the obtained polymer was 116 g, the catalytic activity was u, HIg/gZr-hr, and the apparent bulk specific gravity was 0.
It was 35 g/sJ. Example 4 [Preparation of solid catalyst component] Silica calcined at 800°C for 12 hours (#952 manufactured by Fuji Davison Chemical Co., Ltd.) in a 300 mu glass reaction vessel.
Add 2 g of toluene and 20 ail of toluene to make a suspension.
50 sJl of a toluene solution containing dimethylcyclopentadienyl) zirconium dichloride was added. 3 at 1 temperature
After stirring for 0 minutes, nitrogen was flowed for 2 hours and toluene was distilled off to prepare a solid catalyst component. Example 5 [Polymerization] 50 g of polypropylene powder (manufactured by Chisso Petrochemical Co., Ltd.) and methyl atomized by Tosoh Akzo ■ corresponding to 101 mol of ^l atoms were placed in a gas-phase autoclave made of SuS with an internal volume IL that was sufficiently purged with nitrogen. Kunoxane (molecular weight 99
20sj including 0)! After adding the toluene solution, nitrogen was flowed for 1 hour to distill off the toluene. Next, Example 4
After adding the entire amount of the solid catalyst component prepared in above, the total pressure was adjusted to 10 Kg/cm"G using propylene, and polymerization was carried out at 50°C for 2 hours. After the completion of the polymerization, the total yield of the obtained polymer was , 120g, and the catalyst activity is 7.4Kg/g.
Zr・hr, the apparent bulk specific gravity is 0.45g/cJE, which is not good. Comparative Example 1 [Polymerization] 50 g of polypropylene powder (manufactured by Chisso Petrochemical Co., Ltd.), o, os mmol of dimethylsilylbis(2,4-dimethylcyclo A toluene solution containing 5lsj2 of zirconium dichloride and 20 containing methylal9-noxane manufactured by Tosoh Akzo (molecular weight 990) corresponding to 1019 moles of AI atoms.
After sequentially adding the toluene solution of -1, nitrogen was flowed for 3 hours and toluene was distilled off. Total pressure is 10kg with propylene
/cm"G, and polymerization was carried out at 50°C for 2 hours. After the first polymerization, the total yield of the obtained polymer was 70g.
The catalytic activity is 2.2Kg/gZr-hr, and the apparent bulk specific gravity is 0.35g/sJ! Met.

[Brief explanation of drawings]

1 to 3 are manufacturing process diagrams (flow sheets) for explaining the present invention in detail. that's all

Claims (1)

[Claims] (1) [A] Inorganic particulate carrier, [B] Transition metal compound represented by the general formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (However, M is titanium, zirconium, or hafnium transition metal, Y represents silicon or germanium, R
^1_n-C_5H_4-_n and R^1_q-C_5
H_4_-_q represents an unsubstituted or substituted cyclopentadienyl group, and n and q are integers of 0 to 4, but do not take a value of 0 at the same time. Each R^1 may be the same or different from each other, and represents hydrogen, a silyl group, or a hydrocarbon group, but the position and type of R^1 on the cyclopentadienyl ring are such that there is no plane of symmetry containing M. The arrangement shall be taken. Each R^2 may be the same or different and represents hydrogen or a hydrocarbon group. Further, X may be the same or different, and represents hydrogen, halogen, or a hydrocarbon group. ), [C] aluminoxane, using a solid catalyst component in which either one of [B] and [C], or both [B] and [C] components are supported on [A]. , a method for producing an olefin polymer, which comprises polymerizing an olefin.