KR20140134560A - A catalyst for olefin polymerization and co-polymerization and a method for olefin polymerization and co-polymerization with using the same - Google Patents

Abstract

The present invention relates to a catalyst for olefin polymerization and co-polymerization, and a method for olefin polymerization or co-polymerization using the same, and more specifically, to a high molecular weight catalyst for polyolefin polymerization and co-polymerization, wherein a catalyst component is prepared by using an aluminoxane and metallocene compound supported on a carrier so as to have an excellent catalytic activity and control molecular weight of a polymer greatly, and to a method for olefin polymerization or copolymerization using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst for olefin polymerization and copolymerization, and a process for olefin polymerization or copolymerization using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to olefin polymerization and copolymerization catalysts and olefin polymerization or copolymerization methods using the catalysts. More particularly, the present invention relates to a catalyst for olefin polymerization or copolymerization, The present invention relates to a high molecular weight polyolefin polymerization and copolymerization catalyst which is excellent in the molecular weight of the polymer and whose molecular weight is largely controlled, and relates to an olefin polymerization or copolymerization method using the same.

The metallocenes can generally be represented by the empirical formula L _n MQ _p , where M is a metal of group IIIB, IVB, VB or VIB; Q is a hydrocarbyl group having 1 to 20 carbon atoms or halogen; p is the valence of M-2, and L is the ligand bound to the metal M. The metallocene compound is used in combination with a promoter, methylaluminoxane (MAO), to prepare an olefin polymer or copolymer. Methyl aluminoxanes (hereinafter referred to as " MAO ") include linear and / or cyclic methyl aluminoxane oligomers, wherein methylaluminoxane is linear methyl aluminoxane oligomer, ) -O) _n- AlR ₂ , and when it is a cyclic methylaluminoxane oligomer, it is represented by the formula (-Al (R) -O-) _m , wherein R is a C 1 -C 8 alkyl group, preferably methyl , n is 1 to 40, preferably 10 to 20, and m is 3 to 40, preferably 3 to 20. Methyl aluminoxane is usually prepared by reacting trimethyl aluminum with water or by reacting with hydrated inorganic salts such as CuSO ₄ .H ₂ O or Al ₂ (SO ₄ ) ₃ .H ₂ O. Methylaluminoxane can also be produced in situ in a polymerization reactor by adding trimethylaluminum and water or hydrated inorganic salts to the polymerization reactor. Methyl aluminoxane is a mixture of oligomers having a very high molecular weight distribution, and usually has an average molecular weight of about 900 to 1200. Methyl aluminoxane is usually maintained in solution in toluene.

The metallocene catalyst should be supported on a suitable support for use in a fluidized bed reactor or slurry reactor, and the individual catalyst particles carrying the metallocene should exhibit sufficient activity to avoid problems due to catalyst support residues. One of the typical methods for preparing metallocene supported catalyst that is currently being developed and used is a method in which a metallocene catalyst is supported on silica together with methylaluminoxane (U.S. Patent No. 4,808,561, U.S. Patent No. 4,897,455, U.S. Patent No. 5,240,894 See also

This method is a method in which a hydroxyl group of silica is reacted with methylaluminoxane to support methylaluminoxane on the surface of silica, and the metallocene catalyst is supported on the supported methylaluminoxane. The metallocene catalyst component may be carried at the same time as methylaluminoxane, or may be carried through additional reaction after methylaluminoxane is supported. The activity of the supported catalyst is proportional to the amount of metallocene component supported and also proportional to the loading of methylaluminoxane to assist in supporting the metallocene catalyst component. Methylaluminoxane not only helps to support the metallocene catalyst but also protects the metallocene catalyst component from the catalyst poison. Therefore, the loading amount of methylaluminoxane directly affects the activity of the catalyst.

The activity of the supported metallocene catalyst is a major factor directly affecting the economics of the catalyst. However, in most cases, when the catalyst is supported in the above manner, the catalytic activity of the metallocene catalyst is much lower than that of the non-supported catalyst. Therefore, there are many catalysts that do not satisfy the economical efficiency of the catalyst depending on the type of the catalyst. In addition, one of the major factors in the availability of supported metallocene catalysts is the ability to produce the high molecular weight required under commercial operating conditions during polymerization using a supported catalyst. In the case of many metallocene catalysts, it may not be possible to produce the required high molecular weight polyolefin necessary under commercial operating conditions, especially in the presence of hydrogen for molecular weight control. In this case, even if the economical efficiency of the catalyst is excellent, the value as a catalyst is inevitably lowered.

Many studies have been conducted to increase the catalytic activity of such supported metallocene catalysts. For example, a method of reacting an organosilicon compound with silica to prepare a functional silica carrier and then reacting the MAO with a metallocene compound to prepare a catalyst (U.S. Patent No. 4874734, U.S. Patent No. 5206199, Makromol. Chem., 2003, 197, 233), an organotin compound is reacted with silica and a catalyst, A method of preparing a functional silica support by reacting MAO with a metallocene compound to prepare a catalyst (US Patent No. 6,908,876, European Patent No. 1613667 A2, WO 2004094480 A2, Makromol. Reaction Eng., 2008 , 2, 339, J. Appl. Polym. Sci., 2007, 106, 3149), silicon tetrachloride (SiCl ₄ ) with silica to prepare a functional silica carrier, which is then reacted with a metallocene compound (Makromol. Rapid Commun., 2002, 23, 672), a mixture of MAO and Diol (Bisphenol A) The like have been reported by the use of body-supported metallocene catalyst in this metal supported on silica (European Patent No. 0685494). When an improved metallocene supported catalyst is prepared by these methods, the activity of the catalyst is improved depending on the Lewis acidity of the organosilicon compound or the organotin compound used. However, depending on the influence of the acidity, The rate of chain termination reaction increases rather than the rate, so that the molecular weight produced tends to decrease. Therefore, it is disadvantageous in that it is difficult to produce a polyolefin having a sufficient high molecular weight, which is necessary under a commercial operating condition in the presence of hydrogen for molecular weight control.

On the other hand, studies have been made to improve the catalytic performance by adding a metallocene catalyst at the time of polymerization reaction of an organic compound as a Lewis base and MAO. For example, a method of charging with MAO in the polymerization reaction of tetrahydrofuran, ethyl benzoate, and acetonitrile (J. Polym. Sci., Part A: Polym. Chem. (US Pat. No. 6,933,930, US Pat. Nos. 6,642,326 (1991), 29, 1595), a method of charging with hydrosilane such as tBuMe ₂ SiH, Et ₃ SiH, and poly (hydromethylsiloxane) And so on. Although these methods have been reported to be effective in increasing the molecular weight of the catalyst, they have the disadvantage of reducing the activity of the catalyst and thus reducing the economics of the catalyst.

The problem of improving the activity and the molecular weight of the supported metallocene catalyst can be solved by designing and synthesizing the metallocene catalyst itself, which has excellent activity due to the problem of the metallocene catalyst itself and has a large molecular weight. However, designing and synthesizing such a new metallocene catalyst requires a great deal of time and effort, and its success rate is very low. Accordingly, there is a need for an improved catalyst and a catalyst production method for appropriately improving the supported metallocene catalyst to increase the activity and the molecular weight of the catalyst.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a catalyst for olefin polymerization and copolymerization which is produced through a very simple process and has excellent catalytic activity.

It is still another object of the present invention to provide an olefin polymerization or copolymerization method capable of producing high molecular weight olefin polymers and copolymers by using the catalyst of the present invention.

The catalyst for olefin polymerization and copolymerization according to the invention is characterized in that it is prepared by a process comprising the steps of:

(1) a step of supporting an aluminoxane, an alkoxysilane compound, a metallocene compound, and a titanocene compound or a half-titanocene compound on a carrier,

(2) washing the supported catalyst obtained in the step (1) with an organic solvent; And

(3) drying the catalyst washed in the step (2) and recovering it as a catalyst powder.

In the present invention, in the carrying process of the step (1), a solution obtained by dissolving a metallocene compound, a titanocene compound or a half-titanocene compound in an aluminoxane solution reacted with an alkoxysilane compound is added to the carrier slurry, (Carrying (a) process),

Alternatively, in the carrying process of the step (1), the aluminoxane solution reacted with the alkoxysilane compound is added to the carrier slurry and stirred to carry the aluminoxane and the alkoxysilane compound, and then the metallocene compound and the titanocene compound or the half- (B)), and the mixture is stirred to carry the metallocene component and the titanocene compound or the half-titanocene compound (supporting process (b)).

The metallocene compound to be used in the step (1) is not particularly limited, but a preferable example is a dicyclopentadienyl metallocene or a bridged metallocene or a monocyclopentadienyl metallocene. .

First, dicyclopentadienyl metallocene can be represented by the following general formula (1).

(CpR _n ) (CpR ' _m ) ML _q (1)

Wherein Cp is cyclopentadienyl, indenyl, or fluorenyl,

R and R 'each independently represent hydrogen, alkyl, alkylether, allylether, phosphine or amine,

L represents alkyl, allyl, arylalkyl, amide, alkoxy or halogen,

M represents a transition metal of Group 4 or Group 5 of the periodic table,

n is an integer satisfying 0? n <5, m is 0? m <5, and q is 1? q? 4.

The bridge-bound metallocene can be represented by the following general formula (2).

Q (CpR _n ) (CpR ' _m ) ML _q (2)

Q is a bridging bond between the C rings and may be a divalent linkage such as dialkyl, alkylaryl (Alkylaryl), diarylsilyl ( Diaryl silicon or a hydrocarbon group of 1 to 20 carbon atoms, n is an integer satisfying 0? N <4, m is 0? M <4, and q is 1? Q?

The monocyclopentadienyl metallocene can be represented by the following general formula (3).

　　　‥‥‥ (3)

(3)

(C ₅ H _{5 -y- x} R _x ) represents the number of substituents attached to the cyclopentadienyl, x is 0, 1, 2, 3 or 4, and y is 0 or 1. R represents a substituent having 1 to 20 non-hydrogen atoms consisting of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen or a multifunctional group thereof, Y 'represents -O-, -S -, -NR * -, or -PR * - (wherein R * represents hydrogen, a hydrocarbon group having 1 to 12 carbon atoms), a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, of 6 to 20 carbon atoms halogenated an aryl group or a all-in-one, Z is _{SiR * 2, CR * 2,} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * ₂ or GeR * ₂ , R * is as defined above, L is independently selected from the group consisting of halide, hydrocarbon group of 1 to 20 carbon atoms, hydrocarbyloxy group of 1 to 18 carbon atoms, hydrocarbyl of 1 to 19 carbon atoms An amino group, a hydrocarbyl amide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbylsulfide group having 1 to 18 carbon atoms, Or two substituents L together represent a neutral conjugated diene or a divalent group having 1 to 30 carbon atoms, M represents a group of a group 4 or 5 of the periodic table, It represents a transition metal.

Examples of the dicyclopentadienyl metallocene represented by the general formula (1) include bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadiene (Pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, (2-phenylindenyl) zirconium dimethyl, cyclopentadienyl (2-phenylindenyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, bis Bis-cyclopentadienyl metallocene such as dimethyl, etc.,

Examples of the bridged metallocene represented by the general formula (2) include dimethylsilylbis (1-indenyl) zirconium dimethyl, dimethylsilyl (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, dimethyl Dimethylsilylbis (1-indenyl) zirconium dimethyl, dimethylsilyl (9-fluorenyl) (1-indenyl) zirconium dimethyl, dimethylsilylbis (1- cyclopentadienyl) hafnium dimethyl, dimethylsilylbis (1-cyclopentadienyl) hafnium dimethyl, dimethylsilyl (9-fluorenyl) (1-indenyl) hafnium dimethyl, ethylene bis Zirconium dimethyl, ethylenbis (1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis Indenyl) zirconium dimethyl, ethylene bis (5-methyl-1-indenyl) zirconium dimethyl, ethylene bis (6-methyl- Zirconium dimethyl, ethylenbis (4-phenyl-1-indenyl) zirconium dimethyl, ethylenebis (5-methoxy-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, ethylene bis (4,7-dimethyl-1-indenyl) zirconium dimethyl, ethylene bis Dimethyl bis (trimethylcyclopentadienyl) zirconium dimethyl, ethylene bis (5-dimethylamino-1-indenyl) zirconium dimethyl, ethylene bis (6-dipropylamino-1-indenyl) zirconium dimethyl, 1-indenyl) zirconium dimethyl, ethylenbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, ethylene (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, ethylene (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, ethylene (4-butylthio- (1-cyclopentadienyl) hafnium dimethyl, ethylene bis (1-indenyl) hafnium dimethyl, ethylene bis (4,5-dienyl) zirconium dimethyl, ethylene bis (9-fluorenyl) zirconium dimethyl, Indenyl) hafnium dimethyl, ethylenbis (4-methyl-1-indenyl) hafnium dimethyl, ethylene bis (5-methyl- Methyl-1-indenyl) hafnium dimethyl, ethylenbis (7-methyl-1-indenyl) hafnium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) hafnium dimethyl, ethylene bis (4,7-dimethoxy-indenyl) hafnium dimethyl, ethylene bis (1-indenyl) hafnium dimethyl, ethylene bis (trimethylcyclopentadienyl) hafnium dimethyl, ethylene bis (5-dimethylamino-1-indenyl) hafnium dimethyl, ethylene bis (Dimethylamino) hafnium dimethyl, ethylenbis (5-diphenylphosphino-1-indenyl) hafnium dimethyl, ethylene (1-dimethylamino) 9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, ethylene (4-butylthio-9-fluorenyl) (1- cyclopentadienyl) hafnium dimethyl, ethylene (1- cyclopentadienyl) hafnium dimethyl, ethylene bis (9-fluorenyl) hafnium dimethyl, 2,2-propyl bis (1-cyclopentadienyl) zirconium dimethyl, 2,2- (4-methyl-1-indenyl) zirconium dimethyl, 2,2-bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, Propylbis (7-methyl-1-indenyl) zirconium dimethyl, 2,2-propylbis - indenyl) zirconium dimethyl, 2,2-propylbis (4-phenyl-1-indenyl ) Dimethylzirconium dimethyl, 2,2-propylbis (5-methoxy-1-indenyl) zirconium dimethyl, (4,7-dimethoxy-1-indenyl) zirconium dimethyl, 2,2-propylbis (trimethylcyclopentadienyl) Zirconium dimethyl, 2,2-propylbis (5-dimethylamino-1-indenyl) zirconium dimethyl, 2,2- Bis (dimethylamino) -1-indenyl) zirconium dimethyl, 2,2-propylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, 2-propyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, 2, 2-propyl (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, (1-cyclopentadienyl) hafnium dimethyl, 2,2-propylbis (1-indenyl) hafnium dimethyl, 2,2-propylbis (4-methyl-1-indenyl) hafnium dimethyl, 2,2-propylbis (5-methyl-1-indenyl) hafnium dimethyl, 2,2- -Indenyl) hafnium dimethyl, 2,2-propylbis (6-methyl-1-indenyl) hafnium dimethyl, 2,2- (5-methoxy-1-indenyl) hafnium dimethyl, 2,2-propylbis (2,3-dimethyl- 2-propylbis (4,7-dimethoxy-1-indenyl) hafnium dimethyl, 2,2-dimethylbiphenyl, 2-propylbis (trimethylcyclopentadienyl) hafnium dimethyl, 2,2-propylbis (5-dimethylamino-1-indenyl) hafnium dimethyl, (Dimethylamino) -1-indenyl) hafnium dimethyl, 2,2-propylbis (5-diphenylphosphino-1 (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, 2,2-propyl (4-butylthio-9-fluoro (1-cyclopentadienyl) hafnium dimethyl, 2,2-propylbis (9-fluorenyl) hafnium dimethyl, (1-cyclopentadienyl) zirconium dimethyl, diphenylmethylbis (1-indenyl) zirconium dimethyl, diphenylmethylbis (4,5,6,7-tetrahydro-1-indenyl (1-indenyl) zirconium dimethyl, diphenylmethylbis (4-methyl-1-indenyl) zirconium dimethyl, diphenylmethylbis Dimethyl) zirconium dimethyl, diphenylmethylbis (7-methyl-1-indenyl) zirconium Dimethyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (4-phenyl-1-indenyl) zirconium dimethyl, diphenylmethylbis Indenyl) zirconium dimethyl, diphenylmethylbis (4,7-dimethyl-1-indenyl) zirconium dimethyl, diphenylmethylbis (4,7-dimethoxy- Diphenylmethyl-bis (6-dipropylamino-1-indenyl) zirconium dimethyl, diphenylmethylbis (5-dimethylamino-1-indenyl) zirconium dimethyl, (1-dimethylamino-9-naphthyl) zirconium dimethyl, diphenylmethylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, diphenylmethyl Dimethylcyclopentadienyl) zirconium dimethyl, diphenylmethyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylmethyl (1-cyclopentadienyl) zirconium dimethyl, diphenylmethylbis (9-fluorenyl) zirconium dimethyl, diphenylmethylbis (1-cyclopentadienyl) hafnium dimethyl, diphenylmethylbis Indenyl) hafnium dimethyl, diphenylmethylbis (4,5,6,7-tetrahydro-1-indenyl) hafnium dimethyl, diphenylmethylbis (4-methyl- Diphenylmethylbis (7-methyl-1-indenyl) hafnium dimethyl, diphenylmethylbis (6-methyl-1-indenyl) hafnium dimethyl, diphenylmethylbis (5-methoxy-1-indenyl) hafnium dimethyl, diphenylmethylbis (2,3-dimethyl-1-indenyl) hafnium (4,7-dimethoxy-1-indenyl) hafnium dimethyl, diphenylmethylbis (trimethylcyclopentadienyl) hafnium dimethyl, diphenylmethylbis Yl) hafnium dimethyl, di (Dimethylamino) hafnium dimethyl, diphenylmethylbis (6-dipropylamino-1-indenyl) hafnium dimethyl, diphenylmethylbis (4,7-bis Diphenylmethylphosphino-1-indenyl) hafnium dimethyl, diphenylmethyl (1-dimethylamino-9-fluorenyl) (1- (1-cyclopentadienyl) hafnium dimethyl, diphenylmethyl (4-butylthio-9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylmethyl (1-cyclopentadienyl) zirconium dimethyl, diphenylsilylbis (1-indenyl) zirconium dimethyl, diphenylsilylbis (4-methylcyclopentadienyl) zirconium dimethyl, diphenylmethylbis (5-methyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (4-methyl-1-indenyl) zirconium dimethyl, diphenylsilylbis Dimethyl, Diphenylsilylbis (4-phenyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (7-methyl-1-indenyl) zirconium dimethyl, diphenylsilylbis , Diphenylsilylbis (5-methoxy-1-indenyl) zirconium dimethyl, diphenylsilylbis (2,3-dimethyl-1-indenyl) zirconium dimethyl, diphenylsilylbis (4,7-dimethoxy-1-indenyl) zirconium dimethyl, diphenylsilylbis (trimethylcyclopentadienyl) zirconium dimethyl, diphenylsilylbis (5-dimethylamino Diphenylsilylbis (4,7-bis (dimethylamino) -1-indenyl) zirconium dimethyl (diphenylsilylbis (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylsilylbis (5-diphenylphosphino-1-indenyl) zirconium dimethyl, diphenylsilyl (1-cyclopentadienyl) zirconium dimethyl, diphenylsilyl (9-fluorenyl) (1-cyclopentadienyl) zirconium dimethyl, diphenylsilylbis (9-fluorenyl) zirconium dimethyl, diphenylsilylbis (1-cyclopentadienyl) hafnium dimethyl, diphenylsilylbis (1-indenyl) hafnium dimethyl, diphenylsilylbis (5-methyl-1-indenyl) hafnium dimethyl, diphenylsilylbis (4-methyl-1-indenyl) hafnium dimethyl, diphenylsilylbis (4-phenyl-1-indenyl) hafnium dimethyl, diphenylsilylbis (7-methyl-1-indenyl) hafnium dimethyl, diphenylsilylbis Diphenylsilylbis (2,3-dimethyl-1-indenyl) hafnium dimethyl, diphenylsilylbis (4,7-dimethyl-1-indenyl) Hafnium dimethyl, diphenylsilylbis (4,7-dimethy (5-dimethylamino-1-indenyl) hafnium dimethyl, diphenylsilylbis (trimethylcyclopentadienyl) hafnium dimethyl, diphenylsilylbis 1-indenyl) hafnium dimethyl, diphenylsilylbis (4,7-bis (dimethylamino) -1-indenyl) hafnium dimethyl, diphenylsilylbis (5-diphenylphosphino- ) Hafnium dimethyl, diphenylsilyl (1-dimethylamino-9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylsilyl (4-butylthio-9-fluorenyl) Dienyl) hafnium dimethyl, diphenylsilyl (9-fluorenyl) (1-cyclopentadienyl) hafnium dimethyl, diphenylsilylbis (9-fluorenyl) hafnium dimethyl,

Examples of the monocyclopentadienyl metallocene represented by the general formula (3) include [(Nt-butylamide) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butylamide) (tetramethyl-? 5-cyclopentadienyl) -dimethylsilane] titanium dimethyl, [(N-methylamide) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl ] Tetramethyl-η5-cyclopentadienyl) -dimethylsilane] titanium dimethyl, [(N-phenylamide) (tetramethyl- eta 5 -cyclopentadienyl) ] Dimethyldimethyl, [(N-benzylamide) (tetramethyl-? 5-cyclopentadienyl) -dimethylsilane] titanium dimethyl, (N-methylamido) (? 5-cyclopentadienyl) [(N-butylamido) (η5-indenyl) -dimethylsilane] titanium dimethyl, [(N-methylamido) (η5-cyclopentadienyl) -dimethylsilane] titanium dimethyl, Benzylamide) (eta &lt; 5 &gt; - Dimethylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyl tert-butylcyclopentane, dimethylsilyltrimethylcyclopentadienyl-tert-butylamidozirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl- Diethyl-tert-butylamidozirconium dimethyl, dimethylsilyl tert-butylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyltrimethylsilylcyclopentadienyl-tert-butylamidozirconium dimethyl, dimethylsilyltetramethyl Cyclopentadienyl-phenylamidozirconium dimethyl, dimethylsilyl tetramethylcyclopentadienyl-phenylamido hafnium dimethyl, methylphenylsilyl tetramethylcyclopentadienyl-phenylamidozirconium dimethyl, methylphenylsilyl tetramethylcyclopentadienyl- Phenylamido hafnium dimethyl, methylphenylsilyl tert-butyl cyclopentadienyl -tert-butylamidosyl Dimethyldimethyl, methylphenylsilyl tert-butylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyltetramethylcyclopentadienylpn-phenylamidozirconium dimethyl, dimethylsilyltetramethylcyclopentadienylpn-phenyl Amido hafnium dimethyl, dibromobis triphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1,2-bisdiphenylphosphinoethane ) Nickel, dibromo (1,3-bisdiphenylphosphinoethane) nickel, dibromo (1,1'-diphenylbisphosphinoferrocene) nickel, dimethylbis diphenylphosphine nickel, Bis (diphenylphosphino) ethane) nickel, methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, (2-diphenylphosphino-1- phenylethyleneoxy) phenylpyridine nickel, dichlorobis Triphenylphosphine palladium, dichlorodiacetonitrile Palladium, bis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium bis (tetrafluoroborate), bis (2,2'-bipyridine) methyl iron tetrafluoroborate etherate, The "dimethyl" portion of each of the titanium, zirconium, and hafnium compounds listed above is referred to as -dichloro, -dibromo, -diiodide, -diethyl, -dibutyl, -dibenzyl, -diphenyl, - (N, N-dimethylamino) benzyl, 2-butene-1,4-diyl, -s-trans-eta4-1,4-diphenyl-1,3-butadiene, -Methyl-1,3-pentadiene, -s-trans-eta4-1,4-dibenzyl-1,3-butadiene, -s- trans-eta4-2,4-hexadiene, -S-trans-eta4-1,4-ditolyl-1,3-butadiene, -s-trans-eta4-1,4-bis (trimethylsilyl) -1,3-butadiene -s-cis-? 4-1,4-diphenyl-1,3-butadiene, -s-cis-? 4-3-methyl-1,3-pentadiene, Dibenzyl-1,3-butadiene, -s-cis- Cis-η4-1,3-pentadiene, -s-cis-η4-1,4-ditolyl-1,3-butadiene, -s-cis-η4-1,4-bis (trimethyl Silyl) -1,3-butadiene, and the like.

The catalyst system of the present invention uses the metallocene catalyst component as described above, but may include at least one metallocene catalyst component as described above. In addition, additional catalysts and, if necessary, further catalyst components other than the metallocene catalyst component according to the present invention may be further included.

The metallocene compounds used in the present invention may be prepared by methods well known in the art or may be prepared by methods such as mCAT GmBH (see www.mcat.de) or Strem (see www.strem.com) or Boulder Scientific (see www.bouldersci.com ) Can be used.

The titanocene compound or the half titanocene compound used in the step (1) of the present invention is a compound having hydrogenation performance. Compounds having hydrogenation performance are compounds which lower the hydrogen concentration in a polymerization reactor by hydrogenating ethylene or an -olefin used in the polymerization system. It is advantageous that these compounds inhibit the polymerization reaction and do not deteriorate the performance of the catalyst. A compound having such hydrogenation reaction performance is a compound containing nickel, palladium, ruthenium, platinum or the like, or a metallocene compound having a simple structure. In the present invention, a titanocene compound or a half-titanocene compound having a sufficient hydrogenation reaction performance at a polymerization temperature is advantageous. The titanocene compound or the half titanocene compound may be used alone or in combination with an organometallic compound such as organoaluminum, organolithium, or organomagnesium.

The amount of the compound having the hydrogenation reaction property used in the present invention is 0.03 to 300 moles per mole of the transition metal compound contained in the supported solid catalyst. When the amount of the compound having the hydrogenation reaction performance is less than 0.03 mol, it is difficult to obtain the effect of increasing the molecular weight sufficiently, and when it exceeds 300 mol, the polymerization activity is largely lowered and the molecular weight becomes too large.

The titanocene compound or the half titanocene compound, which is a compound having a sufficient hydrogenation reaction property, used in the present invention, can be represented by the following general formula (4).

(CpR _n ) (CpR ' _m ) TiL _q (4)

Wherein Cp represents cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl,

R and R 'each independently represent hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkylether, an alkylsilyl, an allylether, an alkoxyalkyl, a phosphine or an amine,

L represents alkyl, allyl, arylalkyl, amide, alkoxy or halogen,

n is an integer satisfying 0? n <5, m is 0? m <5, and q is 1? q? 4.

Examples of the titanocene or half titanocene compound that satisfies the above general formula (4) include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopenta (Pentamethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (Trimethylsilylcyclopentadienyl) titanium dichloride, bis (1,3-bistrimethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydro Indenyl) titanium dichloride, bis (6-methyl-1-indenyl) titanium dichloride, bis (7-methyl-1-indenyl) titanium dichloride, ) Titanium dichloride, bis (5-methoxy Indenyl) titanium dichloride, bis (2,3-dimethyl-1-indenyl) titanium dichloride, bis (4,7- Dimethoxy-1-indenyl) titanium dichloride, bis (fluorenyl) titanium dichloride and the like

(Cyclopentadienyl) titanium dichloride, (fluorenyl) (cyclopentadienyl) titanium dichloride, (fluorenyl) (pentamethylcyclopentadienyl) titanium dichloride, (Pentamethylcyclopentadienyl) titanium dichloride, (indenyl) (fluorenyl) titanium dichloride, (tetrahydroindenyl) (cyclopentadienyl) titanium dichloride, (tetrahydroindenyl) ) (Pentamethylcyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (fluorenyl) titanium dichloride, (cyclopentadienyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride , (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (indenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (fluorene Nyl) (1,3-bis Methylsilylcyclopentadienyl) titanium dichloride, and the like.

The "dichloride" moiety of the titanium compounds enumerated above can also be prepared by reacting a "dichloride" moiety of the titanium compound listed above with a dibromo-diiodide, -dimethyl, -diethyl, -dibutyl, -dibenzyl, (N, N-dimethylamino) benzyl, 2-butene-1,4-diyl, -s-trans-eta4-1,4-diphenyl-1,3-butadiene, -s -Trans-eta4-1-dibenzyl-1,3-butadiene, -s-trans-eta4-2,4-hexadiene, -s-trans-? 4-1,3-pentadiene, -s-trans-? 4-1,4-ditolyl-1,3-butadiene, -1,3-butadiene, -s-cis-? 4-1,4-diphenyl-1,3-butadiene, -s- cis-? 4-3-methyl-1,3-pentadiene, cis-cis-cis-? 4-cis-? 4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene, -s-cis-eta4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Examples of the half titanocene compound used in the present invention include cyclopentadienyl titanium trichloride, cyclopentadienyl titanium tripleride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium triiodide, cyclopentadienyl Titanium dichloride, titanium methyldichloride, cyclopentadienyl titanium dimethyl chloride, cyclopentadienyl titanium ethoxydichloride, cyclopentadienyl titanium diethoxy chloride, cyclopentadienyl titanium phenoxide dichloride, cyclopentadienyl titanium diphenoxide chloride , Cyclopentadienyltitanium trimethyl, cyclopentadienyltitanium triethyl, cyclopentadienyltitanium triisopropyl, cyclopentadienyltitanium tri-n-butyl, cyclopentadienyltitanium tri-sec-butyl, cyclopentadienyl Nyltitanium trimethoxide, cyclopenta Cyclopentadienyltitanium tributoxide, cyclopentadienyltitanium triphenyl, cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium tributoxide, cyclopentadienyltitanium tributoxide, cyclopentadienyltitanium tributoxide, cyclopentadienyltitanium tribenzoxide, cyclopentadienyltitanium tributoxide, -m-tolyl, cyclopentadienyltitaniumtri-p-tolyl, cyclopentadienyltitaniumtri-m, p-xylyl, cyclopentadienyltitaniumtri-4-ethylphenyl, cyclopentadienyltitaniumtri- Cyclopentadienyl titanium tri-4-methoxyphenyl, cyclopentadienyl titanium tri-4-ethoxyphenyl, cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium tri-dimethyl amide, cyclopentadienyl titanium tri- Pentadienyl titanium tri-diethyl amide, cyclopentadienyl titanium tri-diisopropyl amide, cyclopentadienyl titanium tri-di-sec-butyl amide, cyclopentadienyl titanium tri- Di-tert-butyl amide, cyclopentadienyl titanium tri-ditriethylsilyl amide, and the like.

The "cyclopentadienyl" moiety of the titanium compounds enumerated above is also referred to as methylcyclopentadienyl, n-butylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, pentamethylcyclopentadienyl, Dienyl, trimethylsilylcyclopentadienyl, 1,3-bistrimethylsilylcyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, 5-methyl- Indenyl, 5-methoxy-1-indenyl, 2,3-dimethyl-1-indenyl, 4,7-dimethyl- 4,7-dimethoxy-1-indenyl, fluorenyl, and the like.

The following half-titanocene compounds are also exemplified.

[(Nt-butylamide) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [(Nt-butylamide) Silane] titanium dichloride, [(N-methylamido) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [ Dimethylsilane] titanium dichloride, [(N-benzylamide) (tetramethyl-η5 (cyclopentadienyl) -dimethylsilane] - (cyclopentadienyl) -dimethylsilane] titanium dichloride, (N-methylamido) (? 5-cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [ Dimethylsilane] titanium dichloride, [(N-benzylamide) (? 5-indenyl) -dimethylsilyl] titanium dichloride, [ It is] such as a titanium dichloride.

The "dichloride" moiety of the half titanocene compounds enumerated above may also be substituted with one or more substituents selected from the group consisting of dibromo, -diiodo, -dimethyl, -diethyl, -dibutyl, -dibenzyl, -diphenyl, -dimethoxy, (N, N-dimethylamino) benzyl, 2-butene-1,4-diyl, -s-trans-eta4-1,4-diphenyl-1,3-butadiene, trans-eta4-3-methyl-1,3-pentadiene, -s-trans-eta4-1,4-dibenzyl-1,3-butadiene, -s- -s-trans-? 4-1,3-pentadiene, -s-trans-? 4-1,4-ditolyl-1,3-butadiene, -s- -1,3-butadiene, -s-cis-? 4-1,4-diphenyl-1,3-butadiene, -s- cis-? 4-3-methyl-1,3-pentadiene, -1,4-dibenzyl-1,3-butadiene, -s-cis-? 4-2,4-hexadiene, -s- cis-? 4-1,3-pentadiene, -1,4-ditolyl-1,3-butadiene, -s-cis-? 4-1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

The titanocene compound and the half titanocene compound may be used alone or in combination. The above-mentioned titanocene compound or half-titanocene compound may be reacted with organoaluminum, organolithium and organomagnesium.

Examples of the organoaluminum which can be used by reacting with the titanocene compound or the half titanocene compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide and the like. Specific examples thereof include trimethylaluminum, triethylaluminum, tributyl Aluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, diethylethoxyaluminum and the like.

Examples of the organolithium that can be used by reacting with the titanocene compound or the half-titanocene compound include compounds represented by the general formula RLi wherein R is an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkylamido group, an allyl group having 6 to 12 carbon atoms, , An arylamido group, an alkyl allyl group having 7 to 20 carbon atoms, an alkyl allyloxy group, an alkyl allyl amide group, an arylalkoxy group, an arylalkyl amide group, and an alkenyl group having 2 to 20 carbon atoms) Specific examples thereof include methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methoxy lithium, isopropoxy lithium, butoxy lithium, dimethyl amide lithium, There may be mentioned lithium, lithium, lithium, lithium, lithium, lithium, lithium, ethylamidium, diisopropylamide lithium, dibutylamidithium, diphenylamidithium, phenyllithium, m-tolylithium, p-tolylithium, xylylithium, methoxyphenyllithium, .

Examples of organomagnesium which can be used by reacting with the titanocene compound or the half titanocene compound include dialkylmagnesium and alkylmagnesium halide. Specific examples thereof include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, diisobutylmagnesium Diethyl magnesium bromide, ethyl magnesium bromide, ethyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, hexyl magnesium bromide, hexyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride, allyl chloride, ethylmagnesium chloride, ethylmagnesium bromide, Magnesium bromide, allyl magnesium chloride, and the like.

The amount of the metallocene catalyst component and the amount of the titanocene compound or the half titanocene compound used in the step (1) of the present invention is preferably 0.05: 1 to 10: 1 by molar ratio. When the amount is less than 0.05: 1, Is too large and the molecular weight is too large. If it exceeds 10: 1, it is difficult to obtain the effect of increasing the molecular weight sufficiently.

The alkoxysilane compound used in the step (1) of the present invention is a silicone compound having an R-O-Si-bond and can be represented by the following general formula (5).

(R'O) _4-n (R) _n Si (5)

Wherein R 'and R represent a hydrocarbon group of 1 to 20 carbon atoms, which may be the same or different from each other, and n is 1, 2 or 3

Examples of the silicon compound having an RO-Si-bond satisfying the above general formula include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, Butoxymethylsilane, diphenylmethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, dipropyldimethoxysilane, Examples of the silane coupling agent include diphenyldimethoxysilane, triphenylmethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, di Ethyl triethoxysilane, ethyl triethoxysilane, isopropyl phosphite triethoxysilane, diisopropyl phosphite diethoxysilane, triisopropyl phosphine ethoxysilane, butyl triethoxysilane, dibutyl diethoxysilane, tri But are not limited to, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilanedimethoxy silane, Silane, diethyldibutoxysilane, ethyltributoxysilane, isopropylpolybutoxysilane, diisopropyldibutoxysilane, triisofluoropropyltoxysilane, butyltributoxysilane, dibutyldibutoxysilane, tri Butylbutoxysilane, phenyltributoxysilane, diphenyldibutoxysilane, triphenylbutoxysilane, and the like.

The amount of the RO-Si-bonded silicon compound used in the step (1) is preferably 0.05 to 10 moles per mole of the metallocene catalyst component contained in the supported solid catalyst. When the amount is less than 0.05 mole, And when it exceeds 10 moles, the polymerization activity is greatly lowered and the molecular weight is greatly lowered, which is not preferable.

The aluminoxane used in the step (1) is at least one selected from linear and cyclic aluminoxane oligomers. When the aluminoxane is a straight chain aluminoxane oligomer, the aluminoxane represented by the formula R- (Al (R) -O) _n -AlR ₂ , and in the case of cyclic aluminoxane oligomers, is represented by the formula (-Al (R) -O-) _m , wherein R is a C1 to C8 alkyl group, preferably methyl, and n is an integer from 1 to 40 , Preferably 10 to 20, and m is 3 to 40, preferably 3 to 20. The aluminoxane is a mixture of oligomers having a very large molecular weight distribution, and usually has an average molecular weight of about 800 to 1200. The aluminoxane solution may contain an aromatic hydrocarbon, an aliphatic hydrocarbon or an aliphatic cyclic hydrocarbon as a solvent, and is preferably used mainly as a solution in toluene. As an example thereof, 10% or 30% methyl aluminoxane produced by Albemarle .

When the step (1) is carried out by the supporting step (a), the concentration of the aluminoxane in the solution obtained in the step (1) is 5 to 30% by weight, (M) is preferably 0.001 to 1.0% by weight. When the concentration of each component is out of the above range, the catalytic activity is too low or too high.

In the process for producing a polyolefin catalyst and a catalyst according to the present invention, the carrier used in the step (1) is a solid particulate porous material, preferably an inorganic material such as silicon and / or aluminum oxide, Is most preferably in the form of spherical particles, for example particles obtained by a spray drying method, and OH groups or other functional groups containing active hydrogen atoms.

The carrier preferably has an average particle size of 10 to 250 占 퐉, preferably an average particle size of 10 to 150 占 퐉, an average diameter of 50 to 500 占 and a micropore volume of 0.1 to 10 ml / g, 0.5 to 5 ml / g, and the surface area of the carrier is 5 to 1,000 m 2 / g, preferably 50 to 600 m 2 / g.

When silica is used as the carrier, at least a part of the active hydroxy [OH] group should be used. The concentration of the hydroxy group is preferably 0.5 to 2.5 mmole or more per 1 g of the silica, more preferably 0.7 to 1.6 mmole / g, If the concentration of the hydroxyl group is less than 0.5 mmole, the amount of aluminoxane supported decreases and the activity decreases. If the concentration is more than 2.5 mmol, the catalyst component is inactivated due to the hydroxyl group, which is not preferable.

The hydroxyl groups of the silica can be detected by IR spectroscopy, and the determination of the hydroxyl group concentration on the silica is carried out by bringing the silica sample into contact with methylmagnesium bromide and measuring the amount of methane foaming (by pressure measurement).

As the silica having the [OH] concentration and the physical properties suitable for the present invention, a silica having a surface area of 300 m &lt; 2 &gt; / g and a pore volume of 1.6 ml / XPO-2410, XPO-2411 and XPO-2412 available from Davison Chemicals Division of Grace &amp; Company, Inc., and dehydrated silica such as Davision 948, 952 and 955 can be used. The desired OH concentration can be used.

In the step (1), when the alumoxane is supported on the support, the metallocene is supported. When the silica is used as the support in the step (1), the hydroxyl group of the silica is anhydrous Under the conditions, it reacts with aluminoxane to support the aluminoxane to provide the site where the metallocene is to be carried, and at the same time, it acts to protect the metallocene, which is liable to lose its activity by being very sensitive to external catalyst poison . Therefore, the higher the amount of supported aluminoxane, the higher the loading of metallocene, the higher the probability of not poisoning by the external catalyst poison, and the higher the activity.

In the step (1), the carrier is used as a carrier slurry, which is prepared by suspending a carrier in a hydrocarbon solvent or a hydrocarbon solvent mixture.

The temperature of the supporting process in the step (1) is preferably from 40 to 160 ° C., more preferably from 80 to 120 ° C. If the temperature is outside the above range, the activity decreases and polymer aggregation occurs in the reactor , It is preferable that the holding time is from 30 minutes to 4 hours, more preferably from 1 to 2 hours. If the time is out of the above range, economical efficiency is poor or the reaction is not sufficient, .

In the supported catalyst solution of the step (1), there is a small amount of unreacted aluminoxane and a non-supported metallocene catalyst, and they need to be removed before the drying process. If the unreacted aluminoxane is not removed, The supported catalysts are adhered to each other, causing a problem of poor injection when the catalyst is injected into the polymerization reactor in a dry form. Injection of the agglomerated catalyst causes a local overaction in the reactor to cause problems of sheet and lump formation . In addition, the metallocene is easily separated from the support during the polymerization reaction to form a very fine particle polymer, thereby causing a problem of fouling of the reactor.

For the purpose of removing such unreformed materials, it is preferable to wash the supported catalyst in the step (2) by an organic solvent such as an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. In the first washing step, the metallocene and aluminoxane are removed. When the supported metallocene is desorbed at this stage, it acts as a factor that lowers the activity of the supported catalyst. Therefore, in order to prevent this, By performing a low-temperature first washing step, the adhesion of the supported metallocene and the aluminoxane component is intensified, thereby preventing detachment of the supported metallocene component in the subsequent secondary washing process. The primary washing temperature is preferably -10 to 60 ° C.

The drying in the step (3) may be carried out using a conventional drying process.

The Al content in the metallocene supported catalyst produced according to the method of the present invention is 10% by weight or more.

The polyolefin polymerization method using the catalyst for polyolefin polymerization produced by the production method according to the present invention is characterized in that hydrogen, olefin and, if necessary, comonomer And then olefin is polymerized or an olefin and a comonomer are copolymerized to prepare an olefin polymer or a copolymer.

Examples of the olefin include ethylene. In this case, the comonomer is preferably an alpha-olefin other than ethylene such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene, The content ratio of the monomer to the ethylene is preferably 0.005 to 0.02, and more preferably 0.008 to 0.015 in terms of the molar ratio of the comonomer / ethylene. In this case, when the molar ratio of comonomer / ethylene is less than 0.005 or exceeds 0.02, a desired level of copolymer can not be obtained, which is not preferable.

In such an olefin (co) polymer preparation process, the metallocene catalyst is combined with at least one activator to form an olefin polymerization catalyst system. Preferred activating agents to be used herein include alkyl aluminum compounds such as diethyl aluminum chloride, aluminoxanes, modified aluminoxanes, neutral or ionic ionizing activators, non-coordinating anions, non-coordinating Group 13 metals or metaloid anions, , And borates.

The alkyl aluminum compound is preferably an alkyl aluminum compound represented by the general formula AlR _n X _(3-n) (wherein R is an alkyl group having 1 to 16 carbon atoms and X is a halogen element and 1? _{N? 3} ) Can be used. Specific examples of the alkylaluminum compound include trialkylaluminums such as triethylaluminum, trimethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, tri-2-methylpentyl Aluminum and the like are used. Particularly preferably, triisobutylaluminum, triethylaluminum, trinormalhexylaluminum or trinormaloctylaluminum is used.

The alkylaluminum compound is preferably used in gas phase polymerization at the following molar ratio depending on the desired polymer properties.

1 ≤ alkyl aluminum compound / transition metal in main catalyst ≤ 1000

More preferably,

10 ≤ alkyl aluminum compound / transition metal in main catalyst ≤ 300

If the molar ratio of the transition metal in the alkylaluminum compound / main catalyst is less than 1, sufficient polymerization activity can not be obtained. On the other hand, if it exceeds 1000, the polymerization activity is adversely affected.

In the above-mentioned olefin (co) polymer production method, the polymerization reaction is preferably carried out at 60 to 120 ° C in the absence of a hydrocarbon solvent, more preferably at 65 to 100 ° C, most preferably at 70 to 80 ° C And is preferably carried out at 2 to 40 atm, more preferably at 10 to 30 atm.

When the polymerization temperature in the reactor is lower than 60 DEG C, sufficient polymerization efficiency can not be obtained, which is undesirable. If it exceeds 120 DEG C, a polymer mass tends to be easily generated. When the operating pressure in the reactor is lower than 2 atmospheres, the ethylene partial pressure is too low to obtain sufficient polymerization efficiency. When the pressure is higher than 40 atmospheres, it is difficult to control the reaction, It is not preferable.

The metallocene supported catalyst component prepared above as the main catalyst of the present invention can be used in the prepolymerized state with ethylene or an? -Olefin before being used as a component in the polymerization reaction. The prepolymerization can be carried out in the presence of a hydrocarbon solvent such as hexane at a sufficiently low temperature and in the presence of the catalyst component and an organoaluminum compound such as triisobutylaluminum under ethylene or alpha-olefin pressure conditions. Pre-polymerization helps wrap the catalyst particles around the polymer to maintain the catalyst shape and improve the shape of the polymer after polymerization. The weight ratio of polymer / catalyst after pre-polymerization is usually from 0.1: 1 to 200: 1. Preferred organometallic compounds include trialkylaluminums having alkyl groups of 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and mixtures thereof. In some cases, an organoaluminum compound having at least one halogen or hydride group such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride and the like can be used.

According to the present invention, a metallocene supported catalyst component is prepared by using a metallocene catalyst component, a titanocene or a half titanocene compound, and reacting the aluminoxane with an alkoxysilane compound to further improve catalytic activity and to produce a high molecular weight polyolefin Polymerization and copolymers can be prepared.

In addition, in the present invention, it is possible to provide a catalyst capable of largely maintaining and controlling the molecular weight even under polymerization conditions close to commercial conditions, in particular, in the polymerization or copolymerization using hydrogen as a molecular weight regulator, and the product obtained in the polymerization method using the catalyst of the present invention Is a solid high molecular weight polyolefin homopolymer or copolymer, and the yield of the polymer is sufficiently high to eliminate the need for removal of the catalyst residue, and has excellent apparent density and fluidity.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these embodiments are for illustrative purposes only, and the present invention is not limited to these embodiments.

[Raw material]

Hereinafter, the metallocene catalyst component used in the examples may be produced by the method of the already well-known literature, or may be produced by mCAT GmBH (see www.mcat.de) or Strem (see www.strem.com) or Boulder Scientific (see www. bouldersci.com) were used.

[ Metallocene  Preparation of Supported Catalyst]

Example  One

50 ml of a methylaluminoxane solution (10% by weight) was quantitatively measured in a measuring cylinder, and cyclohexylmethyldimethoxysilane (cyclohexylmethyldimethoxysilane / metallocene = 0.6 mol / mol), which is an alkoxysilane, The reaction was carried out at room temperature for 30 minutes or more. 5 g of dehydrated silica of the trade name XPO-2402 (average particle size to 50 탆, surface area 300 m 2 / g, micropore volume 1.6 ml / g, OH concentration 1 mmol / g, Grace, USA) was quantitated under anhydrous conditions and 20 ml of toluene And the mixture was stirred in a slurry state. This was injected into a 1 L reactor equipped with a stirrer and a cooling condenser. 50 ml of a methylaluminoxane solution (10 wt%, Toluene, Albemarle Company, USA) reacted with the alkoxysilane was quantitatively measured in a measuring cylinder, and then a metallocene catalyst component Et (IND) preliminarily quantified in 250 ml Schlenk ) ₂ to the ZrCl ₂ (metallocene / silica = 140μmol / g silica), and titanocene compound Cp ₂ TiCl _2, (Cp ₂ TiCl ₂ / Si = 30μmol / g silica) with mixing at 5 ~ 10 ℃, and stirred for 15 minutes The solid metallocene catalyst and Cp ₂ TiCl ₂ were dissolved and reacted. The resulting methylaluminoxane-metallocene solution was added to the reactor while maintaining the temperature of the reactor at room temperature. Then, the reaction temperature was elevated to 110 캜 with stirring. At this temperature, the support reaction was allowed to proceed for 90 minutes. After the completion of the reaction, the reaction product was transferred to a Schlenk vessel, and then the upper solution was decanted. After the reaction mixture was stirred at room temperature, the reaction mixture was allowed to stand for 10 minutes and then the upper solution was discharged. The reaction mixture was firstly washed with 100 ml of toluene at room temperature. After the reaction mixture was stirred at room temperature, the reaction mixture was poured into the upper solution and washed with 100 ml of toluene at room temperature. The resulting catalyst system was then washed with purified hexane and then dried under mild vacuum. The amount of the supported catalyst prepared was 9.4 g.

Comparative Example  One

In Example 1, a catalyst was prepared under the same conditions as in Example 1 without using alkoxysilane.

Example  2

In Example 1, the metallocene catalyst component Et (IND) ₂ ZrCl ₂ a (IND) was used to replace it with a ₂ ZrCl ₂ was prepared except that the catalyst in the same conditions as in Example 1.

Comparative Example  2

In Example 2, a catalyst was prepared under the same conditions as in Example 2 without using alkoxysilane.

Example  3

In Example 1, the metallocene catalyst component Et (IND) ₂ was used to replace the ZrCl ₂ (nBuCp) ₂ ZrCl ₂ in other than the A catalyst was prepared in the same conditions as in Example 1.

Comparative Example  3

In Example 3, a catalyst was prepared under the same conditions as in Example 3 without using alkoxysilane.

Example  4

Example 1 In the metallocene catalyst component to metal Et (IND) ₂ ZrCl ₂ a (1,3-Et, MeCp) was used to replace it with a ₂ ZrCl ₂ was prepared except that the catalyst in the same conditions as in Example 1.

Comparative Example  4

In Example 4, a catalyst was prepared under the same conditions as in Example 4, without using alkoxysilane.

Comparative Example  5

In Example 1, a catalyst was prepared under the same conditions as in Example 1, except that Et (IND) ₂ ZrCl ₂ was not used.

Comparative Example  6

In Example 1, a catalyst was prepared under the same conditions as in Example 1 except that Cp ₂ TiCl ₂ (Cp ₂ TiCl ₂ / silica = 200 μmol / g silica) was used instead of Et (IND) ₂ ZrCl ₂ .

[Preparation of Polymer]

Example  5

[Polymerization method]

Polymerization was carried out in the following manner using the supported metallocene supported catalyst under the conditions shown in Table 1. A pressure vessel was placed on the front of a 2 L stainless steel polymerization reactor, filled with hydrogen as shown in Table 1, and the remaining pressure was mixed with ethylene to prepare a mixed gas having a total pressure of 330 psig.

The reactor was charged with 1000 ml of purified hexane and 1-hexene in the amount shown in Table 1. Next, 1.0 cc of a 1 M hexane dilution of triisobutylaluminum (TiBA) as a catalyst poisoning agent was introduced into the reactor, stirred, elevated to 65 캜, and stirring was stopped. 15 to 25 mg of the metallocene supported catalyst prepared in Example 1 as the main catalyst was quantitatively measured in a glove box and transferred to a 5 ml syringe. 1.0 cc of 1 M hexane dilution of triisobutylaluminum (TiBA) as an activator was taken. The activated catalyst slurry was transferred to the reactor and injected into the reactor at 65 ° C. The reactor temperature was then raised to 80 占 폚. The reaction was started by feeding a hydrogen / ethylene mixed gas such that the total pressure of the reactor was 200 psig and then stirring at 1000 rpm. During the reaction, the polymerization reaction was carried out for 20 minutes while supplying a sufficient ethylene / hydrogen mixed gas so that the total pressure of the reactor could be kept constant at 200 psig. After the polymerization for 20 minutes, the injection of the ethylene / hydrogen mixed gas was stopped to terminate the reaction, and the resulting polymer was obtained. The resulting polymer was separated by a filter and sufficiently dried to obtain a polymer. The polymerization results are shown in Table 1.

[Polymer analysis]

The polymer obtained above was subjected to the following analysis.

1) Density (g / mL): Analysis was performed based on ASTM1505.

2) Melt Index (MI), 190 DEG C, 2.16 Kg, g / 10 min.): Analysis was carried out on the basis of ASTM1238.

Example  6

Polymerization was carried out under the same conditions as in Example 5, except that the catalyst of Example 2 was used. The polymerization conditions and polymerization results are shown in Table 1.

Example  7

Polymerization was carried out under the same conditions as in Example 5 except that the catalyst of Example 3 was used. The polymerization conditions and polymerization results are shown in Table 1.

Example  8

Polymerization was carried out under the same conditions as in Example 5 except that the catalyst of Example 4 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  7

Polymerization was carried out under the same conditions as in Example 5 except that the catalyst of Comparative Example 1 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  8

Polymerization was carried out under the same conditions as in Comparative Example 7, except that the catalyst of Comparative Example 2 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  9

Polymerization was carried out under the same conditions as in Comparative Example 7, except that the catalyst of Comparative Example 3 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  10

Polymerization was carried out under the same conditions as in Comparative Example 7, except that the catalyst of Comparative Example 4 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  11

Polymerization was carried out under the same conditions as in Comparative Example 7, except that the catalyst of Comparative Example 5 was used. The polymerization conditions and polymerization results are shown in Table 1.

Comparative Example  12

Polymerization was carried out under the same conditions as in Comparative Example 7 except that the catalyst of Comparative Example 6 was used. The polymerization conditions and polymerization results are shown in Table 1.

Example  9

　　　　 In the same manner as in Example 1, except that diisopropyldimethoxysilane (diisopropyldimethoxysilane / metallocene = 0.6 mol / mol) was used instead of cyclohexylmethyldimethoxysilane, which is an alkoxysilane, And polymerization was carried out under the same conditions as in Example 5. [ The results are shown in Table 1.

Example  10

A catalyst was prepared under the same conditions as in Example 1, except that isobutyltriethoxysilane (isobutyltriethoxysilane / metallocene = 0.6 mol / mol) was used instead of cyclohexylmethyldimethoxysilane, which is an alkoxysilane , And the polymerization was carried out under the same conditions as in Example 5. The results are shown in Table 1.

Example  11

A catalyst was prepared under the same conditions as in Example 1, except that diphenyldimethoxysilane (diphenyldimethoxysilane / metallocene = 0.6 mol / mol) was used instead of cyclohexylmethyldimethoxysilane which was an alkoxysilane , And the polymerization was carried out under the same conditions as in Example 5. The results are shown in Table 1.

Example  12

A catalyst was prepared under the same conditions as in Example 1, except that methyltrimethoxysilane (methyltrimethoxysilane / metallocene = 0.6 mol / mol) was used instead of cyclohexylmethyldimethoxysilane, which is an alkoxysilane, , And the polymerization was carried out under the same conditions as in Example 5. The results are shown in Table 1.

Example  13

A catalyst was prepared under the same conditions as in Example 1, except that phenyltriethoxysilane (phenyltriethoxysilane / metallocene = 0.6 mol / mol) was used instead of cyclohexylmethyldimethoxysilane which was an alkoxysilane , And the polymerization was carried out under the same conditions as in Example 5. The results are shown in Table 1.

catalyst C6
(mL) Amount of hydrogen
(mL) activation
(g polymer / g catalyst / hr) Melt Index
(2.16 Kg, g / 10 min.) density
(g / mL) Example 5 Example 1 50 30 15200 1.4 0.917 Comparative Example 7 Comparative Example 1 50 30 6800 1.5 0.917 Example 6 Example 2 70 50 8200 0.17 0.917 Comparative Example 8 Comparative Example 2 70 50 4000 0.16 0.918 Example 7 Example 3 70 50 11400 0.09 0.916 Comparative Example 9 Comparative Example 3 70 50 5800 0.10 0.917 Example 8 Example 4 70 50 5700 0.06 0.919 Comparative Example 10 Comparative Example 4 70 50 2800 0.07 0.918 Comparative Example 11 Comparative Example 5 70 50 N.A. - - Comparative Example 12 Comparative Example 6 70 50 N.A. - - Example 9 Example 9 70 50 13500 1.2 0.917 Example 10 Example 10 70 50 13700 1.3 0.918 Example 11 Example 11 70 50 15800 1.2 0.916 Example 12 Example 12 70 50 12700 1.1 0.917 Example 13 Example 13 70 50 14600 1.3 0.916

*) NA = No Activity

As shown in Table 1, the catalysts prepared using aluminoxane reacted with the alkoxysilane compounds of Examples 1 to 4 had a melt index (Mw), which is a molecular weight index, as compared with the catalysts of Comparative Examples 1 to 4 in which no alkoxysilane compound was used (MI) is also kept low (the lower the melt index, the higher the molecular weight) and the catalyst activity is very good. In addition, it can be seen that the supported catalysts of Examples 1 to 4 are maintained similar to the catalysts of Comparative Examples 1 to 4 in terms of density. Even when aluminoxane reacted with various kinds of alkoxysilane compounds was used in Examples 9 to 13, the melt index (MI), which is a molecular weight index, was kept low and the catalytic activity was more excellent. On the other hand, in the case of Comparative Examples 11 to 12, it can be seen that no catalytic activity is observed. That is, it can be seen that no useful catalyst is formed when only the titanium compound is used without using the above metallocene component.

Claims (8)

A catalyst for olefin polymerization or copolymerization prepared according to a process comprising the steps of:
(1) a step of supporting an aluminoxane, an alkoxysilane compound, a metallocene compound, and a titanocene compound or a half-titanocene compound on a carrier,
Here, the metallocene compound is selected from compounds represented by the following general formulas (1) to (3), and the titanocene compound or the half-titanocene compound is a compound represented by the following general formula (4) And the alkoxysilane compound is selected from compounds represented by the following general formula (5)
(CpR _n ) (CpR ' _m ) ML _q (1)
Wherein Cp is cyclopentadienyl, indenyl, or fluorenyl,
R and R 'are each independently hydrogen, alkyl, alkyl ether, allyl ether, phosphine or amine,
L represents alkyl, allyl, arylalkyl, amide, alkoxy or halogen,
M represents a transition metal of Group 4 or Group 5 of the periodic table,
n is an integer satisfying 0? n <5, m is 0? m <5, q is 1? q? 4;
Q (CpR _n ) (CpR ' _m ) ML _q (2)
Wherein Q is a bridging bond between the C rings and is a dialkyl, alkylaryl, diarylsilyl, or a divalent linking group having 1 to 20 carbon atoms A hydrocarbon group, n is 0? N <4, m is 0? M <4, q is an integer satisfying 1? Q? 4;

(3)
Wherein x is 0, 1, 2, 3 or 4, y is 0 or 1, and R is selected from the group consisting of hydrogen, a hydrocarbon group of 1 to 20 carbon atoms, a silyl group, a germyl group, a cyano group, Y 'represents -O-, -S-, -NR * -, or -PR * - (wherein R * represents hydrogen, a hydrocarbon group of 1 to 12 carbon atoms) , A hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a compound thereof, Z is SiR * ₂ , CR * ₂ , SiR * ₂ SiR * ₂ , CR * ₂ CR * ₂ , CR * = CR *, CR * ₂ SiR * ₂ or GeR * ₂ , R * is as defined above, L is independently selected from halide, A hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 19 carbon atoms, a hydrocarbylamide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a carbon A hydrocarbylsulfide group having 1 to 18 carbon atoms and a multifunctional group thereof, or two substituents L together form a neutral conjugated diene having 1 to 30 carbon atoms or And M represents a transition metal of Group 4 or Group 5 of the periodic table;
(CpR _n ) (CpR ' _m ) TiL _q (4)
Cp represents cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl; R and R 'each independently represent hydrogen, a hydrocarbon group of 1 to 20 carbon atoms, an alkyl ether, an alkylsilyl, an allyl ether, N is an integer of 0 to n <5, m is 0 to m <5, and q is an integer of 1 to q? 4 Lt; / RTI &gt;;
(R'O) _4-n (R) _n Si (5)
Wherein R 'and R represent a hydrocarbon group of 1 to 20 carbon atoms, which may be the same or different, and n is 1, 2 or 3;
(2) washing the supported catalyst obtained in the step (1) with an organic solvent; And
(3) drying the catalyst washed in the step (2) and recovering it as a catalyst powder. The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the amount of the metallocene catalyst component and the amount of the titanocene compound or the half titanocene compound used is in the range of 0.05: 1 to 10: 1. The olefin polymerization or copolymerization catalyst according to claim 1, wherein the amount of the alkoxysilane compound used is 0.05 to 10 moles per mole of the metallocene component. The method according to claim 1, wherein the supporting step of (1) is carried out by adding a solution obtained by dissolving a metallocene compound, a titanocene compound or a half-titanocene compound to a solution of aluminoxane reacted with an alkoxysilane compound, And then stirring the mixture. The catalyst for olefin polymerization or copolymerization according to claim 1, The method according to claim 1, wherein the supporting step of (1) is carried out by adding an aluminoxane solution reacted with an alkoxysilane compound to a carrier slurry, stirring the resulting slurry, and adding a metallocene compound and a titanocene compound or a half titanocene compound Wherein the reaction is carried out by adding a compound and stirring. 2. The method of claim 1, wherein the support has micropores having an average particle size of 10 to 250 占 퐉, an average diameter of 50 to 500 占 and a micropore volume of 0.1 to 10 ml / g and a surface area of 5 to 1000 m2 / g Lt; RTI ID = 0.0 &gt; olefin &lt; / RTI &gt; The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the aluminoxane is selected from linear aluminoxane oligomers and cyclic aluminoxane oligomers. A process for olefin polymerization or copolymerization comprising polymerizing an olefin using a catalyst according to any one of claims 1 to 7 or copolymerizing an olefin with a comonomer.