KR101689456B1 - Ethylene-Olefin Copolymer and preparation thereof - Google Patents

Abstract

The present invention relates to an ethylene-based copolymer having a characteristic of having an inflection point in dynamic shear viscosity measurement by introducing a long-chain branch into the copolymer, thereby reducing the load during extrusion processing and increasing the melt strength and improving bubble stability during processing of the blown film to provide.

Description

Ethylenic Copolymer and Preparation thereof < RTI ID = 0.0 > (Ethylene-Olefin Copolymer &

The present invention relates to an ethylenic copolymer excellent in extrusion molding processability. More specifically, the present invention relates to a process for producing an ethylene-based copolymer which provides a long-chain branched introduction of a certain component or more into a linear polyethylene copolymer and induces a broad molecular weight distribution, exhibits low load during extrusion processing, .

The metallocene-based polyethylene resin produced by using the conventional metallocene catalyst provides excellent mechanical properties in film molding due to its molecular characteristics. However, since the molecular weight distribution is narrow, the processing load is high and the possibility of melt fracture in extrusion processing is high. In addition, since the melt strength is low, there is a limitation in industrial applications such as a failure to increase production speed due to bubble instability when processing a wide-width blown film. Therefore, there has been a demand for improving the processability and the melt strength of the metallocene-based polyethylene resin continuously.

 In general, efforts have been made to broaden the molecular weight distribution in order to lower the processing load. In this case, however, the extrusion load is reduced to some extent but the actual melt strength is not improved. Korean Patent Application No. 10-2007-7022531 discloses a method for broadening the molecular weight distribution and the melt strength by mixing a polymer having a high molecular weight, but this method is unsuitable for film applications. In addition, a method of using a heterogeneous catalyst or a method of increasing the molecular weight distribution by a multi-stage reaction (Korean Patent Application No. 10-2000-7008658) has been proposed, but this method is also unsuitable for film applications requiring transparency.

In addition, a method of partially blending a long chain branching resin (such as LDPE) having high melt strength is easily used, which does not prevent deterioration of the mechanical properties of the final product (U.S. Patent No. 6,114,457).

In a more practical method, a method for introducing a long chain brane into a metallocene linear polyethylene resin (U.S. Patent No. 5,272,236, Korean Patent Application No. 10-1999-7007119) has been proposed. However, this method proceeds in such a form that a macromer in the terminal double bond state produced in the polymerization step is inserted and formed in the main chain like the comonomer. Therefore, the macromonomer in the reaction mechanism is limited to the solution process which can easily access the polymerization catalyst active site, and the content of inserted LCB is too low to substantially improve the melt strength.

In addition, a method has been proposed in which a macromer is optionally added to introduce a long-chain branch (Korean Patent Application No. 10-2004-0029640), which is applicable only to a slurry reaction. In the gas phase polymerization, It is impossible to inject macromonomer substantially 1-octene or higher, which is impossible to apply.

And a method of increasing the melt strength through a crosslinking reaction of a further produced polymer has been proposed (U.S. Patent No. 4,714,716) . However, this method has problems such as gelation, difficulty in controlling the melt index, and transparency.

An object of the present invention is to provide an ethylene-based copolymer resin which induces introduction of a long-chain branch into a metallocene-based linear ethylene copolymer, lowers a processing load in extrusion processing, and has high melt strength and high bubble stability at the time of film processing.

The object of the present invention is also to provide an ethylenic copolymer resin suitable for various processing methods because the mechanical properties of the film are not lowered and the processability and the melt strength are higher than those of conventional ethylenic copolymers having the same melt index and density .

In order to achieve the above objects, the present invention provides an ethylene-based copolymer exhibiting unique characteristics different from conventional metallocene-based polyolefin (co) polymers by gas phase polymerization using a metallocene polymerization catalyst system.

The ethylenic copolymer according to the present invention has a melt flow index of 0.1 to 15.0 g / 10 min (at 190 DEG C under a load of 2.16 kg), 2) a density of 0.900 to 0.929 g / mL, 3) The correlation coefficient between the phase angle and the phase modulus of the complex modulus measured by the dynamic shear viscometer is in the range of 2.5 to 6.0 and the correlation coefficient between the phase angle and the complex elastic modulus is the complex elastic modulus And has an inflection point in a range of 10 ³ to 10 ⁷ , and has a phase angle (critical phase angle,? C) of 20 to 70 at an inflection point. The ethylenic copolymer of the present invention has the above-mentioned properties 1) to 4), so that it has excellent processability such as bubble stability at the time of film processing and exhibits an effect of high melt strength.

The ethylenic copolymer according to the present invention preferably has an alpha-olefin content of from 1 to 20% by weight based on the total weight of the copolymer, and the melt index measured at 190 DEG C and 21.6 kg (MI ₂₁ ) measured at 190 ° C and 2.16 kg (MI ₂₁ / MI ₂ ) of the melt index (MI ₂ ) is preferably 15 to 100. When the content of the comonomer and the melt index ratio (MFRR) are out of the above range, the properties of the ethylenic copolymer resin suitable for various processing methods are high because the processability and the melt strength of the film are improved without deteriorating the mechanical properties of the film It is not preferable because it is difficult to exert.

Hereinafter, the contents of the present invention will be described in detail.

When there is no other definition in the technical term used in the present invention, it is understood by those having ordinary skill in the art to which the present invention belongs.

The Critical Phase Angle (δc) used in the present invention is used in a rheological method for comparing polymer materials having different structural characteristics, and the method is particularly applicable to the long chain Brach). This method is also called Van-Gurp Palmen analysis (Rheology Bulletin, 1998, 67, 5-8, 2. Correlations between Molecular Structure and Long-Chain Branched Metallocene Catalyzed Polyethylenes, Macromolecules, 2011, 44 , 5401-5413). (PE) and long-chain branch (PE) through a plot of the phase angle shift (δ) and the complex modulus (G *) obtained from the dynamic frequency sweep measured by the ARES instrument (LCB) structure exhibits different behaviors. In the case of a general linear alpha-olefin copolymer, the phase angle tends to be flattened to approach 90 degrees toward a region having a small complex elastic modulus. However, in the case of a resin containing a long chain branch (LCB), such a general curve is deformed to form an inflection point, which is referred to as a critical phase angle (δ _C ), and as this value is lower, It is known that the content is high. It is interpreted that the formation of such an inflection point is due to the fact that the elasticity of the resin is faster than the linear polymer in the presence of LCB when the complex elastic modulus increases. Detailed analytical methods are detailed in the following examples.

Hereinafter, the ethylenic copolymer of the present invention and its production will be described. Hereinafter, preferred examples of the production method will be described, but the present invention is not limited to such examples.

[ Metallocene  catalyst]

The ethylenic copolymer according to the present invention is prepared by polymerization in a gas-phase reactor using a metallocene catalyst. The ethylenic copolymer used in the present invention, which is an ethylenic copolymer capable of introducing a long- A metallocene catalyst suitable for the preparation of a metallocene catalyst may be prepared by a process comprising the following steps:

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

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

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

In the method for producing the metallocene catalyst, the supporting step of the step (1) may include adding a solution obtained by dissolving a metallocene compound, a titanocene compound or a half titanocene compound in a solution of aluminoxane to a carrier slurry, Followed by stirring (carrying process (a)). Alternatively, the loading reaction of the step (1) may be carried out by adding aluminoxane to the slurry of the support and carrying the aluminoxane onto the support to obtain a slurry of alumoxane-supported carrier obtained by adding the metallocene compound, the titanocene compound or the half- Followed by stirring (carrying (b) process).

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)

Here, Cp, R, R ', M and L have the same meanings as in the general formula (1)

Q is a bridge bond between Cp rings and represents a dialkyl, alkylaryl, 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? 4.

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, 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,

Y 'represents -O-, -S-, -NR * -, or -PR * - wherein R * represents hydrogen, a hydrocarbon group of 1 to 12 carbon atoms, a hydrocarbyloxy group of 1 to 8 carbon atoms, A halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a multifunctional group thereof)

Z represents SiR * ₂ , CR * ₂ , SiR * ₂ SiR * ₂ , CR * ₂ CR * ₂ , CR * = CR *, CR * ₂ SiR * ₂ or GeR * ₂ , The same,

Each L independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, 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 hydrocarbon group having 1 to 18 carbon atoms A hydrocarbylsulfide group having 1 to 18 carbon atoms, a hydrocarbylsulfide group having 1 to 18 carbon atoms, and a multifunctional group thereof, or two substituents L may be bonded together A neutral conjugated diene having 1 to 30 carbon atoms or a divalent group,

M represents a transition metal of group 4 or group 5 of the periodic table.

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 metallocene catalyst system used in the production of the ethylenic copolymer of the present invention may contain at least one metallocene catalyst component as described above although the metallocene catalyst component as described above is used. In addition, additional catalysts and, if necessary, further catalyst components other than the above-mentioned metallocene catalyst components 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 above step (1) can be represented by the following general formula (4).

(CpRn) (CpR'm) TiLq (4)

Wherein Cp is cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl,

Rn and R'm each independently represent hydrogen, a hydrocarbon 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, q is 1? q?

Examples of the titanocene or half titanocene compound which satisfies the above general formula (4) include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (n- (Tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis Bis (trimethylsilylcyclopentadienyl) titanium dichloride, bis (1,3-bistrimethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetra Indenyl) titanium dichloride, bis (6-methyl-1-indenyl) titanium dichloride, bis (7-methyl-1-indenyl) titanium dichloride, Nyl) titanium dichloride, Indenyl) titanium dichloride, bis (2,3-dimethyl-1-indenyl) titanium dichloride, bis (4,7-dimethyl- Titanium dichloride, bis (2,3-dimethoxy-1-indenyl) titanium dichloride, bis (fluorenyl) titanium dichloride and the like, (pentamethylcyclopentadienyl) (cyclopentadienyl) titanium dichloride, (Pentamethylcyclopentadienyl) titanium dichloride, (fluorenyl) (pentamethylcyclopentadienyl) titanium dichloride, (indenyl) (pentamethylcyclopentadienyl) titanium dichloride, (indenyl) (Tetrahydroindenyl) titanium dichloride, (tetrahydroindenyl) (cyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium dichloride, (tetrahydroindenyl) (Phenylenediamine) titanium dichloride, (cyclopentadienyl) (1,3-bis (Pentamethylcyclopentadienyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, (indenyl) (1,3-bistrimethylsilylcyclopentyldimethylsilylcyclopentadienyl) titanium dichloride, (Pentadienyl) titanium dichloride, (fluorenyl) (1,3-bistrimethylsilylcyclopentadienyl) titanium dichloride, and the like.

Also exemplified are compounds in which the "dichloride" moiety of the titanium compound listed above is replaced by a compound of the following list: - dibromo, - diiodo, - dimethyl, - diethyl, Bis-2- (N, N-dimethylamino) benzyl, 2-butene-1,4-diyl, -s-trans-eta4- 1,4-diphenyl-1,3-butadiene, -s-trans-eta4-3-methyl-1,3-pentadiene, -s- trans-eta4-1,4-dibenzyl- , -s-trans-? 4-2,4-hexadiene, -s-trans-? 4-1,3-pentadiene, -s-trans-eta4-1,4-ditolyl-1,3-butadiene, s-trans-eta4-1,4-bis (trimethylsilyl) -1,3-butadiene, -s-cis-eta4-1,4-diphenyl-1,3-butadiene, -Methyl-1,3-pentadiene, -s-cis-? 4-1,4-dibenzyl-1,3-butadiene, -s- cis-? 4-2,4-hexadiene, -1,3-pentadiene, -s-cis-? 4-1,4-ditolyl-1,3-butadiene, -s-cis-eta4-1,4-bis (trimethylsilyl) .

Examples of the half titanocene compound include cyclopentadienyl titanium trichloride, cyclopentadienyl titanium trifluoride, cyclopentadienyl titanium tribromide, cyclopentadienyl titanium triiodide, cyclopentadienyl titanium methyl Cyclopentadienyltriethoxysilane, dichloride, cyclopentadienyltitanium dimethylchloride, cyclopentadienyltitanium ethoxydichloride, cyclopentadienyltitanium diethoxychloride, cyclopentadienyltitaniumphenoxide dichloride, cyclopentadienyltitanium diphenoxydichloride, cyclo Cyclopentadienyl titanium triethyl, cyclopentadienyl titanium tri-isopropyl, cyclopentadienyl titanium tri-n-butyl, cyclopentadienyl titanium tri-sec-butyl, cyclopentadienyl titanium Trimethoxide, cyclopentadienyl Cyclopentadienyltitanium tri-isopentoxide, cyclopentadienyl titanium tributoxide, cyclopentadienyl titanium triphenyl, cyclopentadienyl titanium tribenzyl, cyclopentadienyl titanium tri-m -Cyclopentadienyl titanium tri-4-ethylphenyl, cyclopentadienyl titanium tri-4-hexyl, cyclopentadienyltitanium tri-4-hexyl Phenyl, cyclopentadienyl titanium tri-4-methoxyphenyl, cyclopentadienyl titanium tri-4-ethoxyphenyl, cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium tri-dimethyl amide, cyclopentadienyl Cyclopentadienyl titanium tri-diisopropyl amide, cyclopentadienyl titanium tri-di-sec-butyl amide, cyclopentadienyl titanium tri-di-tert- Butyl amide, cyclopentadienyl titanium tri- and the like di-triethylsilyl-amide.

Also exemplified are compounds in which the "cyclopentadienyl" moiety of the titanium compounds enumerated above is replaced by a compound of the following list: methylcyclopentadienyl, n-butylcyclopentadienyl, 1,3- Dimethylcyclopentadienyl, pentamethylcyclopentadienyl, tetramethylpentadienyl, trimethylsilylcyclopentadienyl, 1,3-bistrimethylsilylcyclopentadienyl, indenyl, 4,5,6,7-tetra Methyl-1-indenyl, 5-methoxy-1-indenyl, 5-methyl-1-indenyl, 1-indenyl, 4,7-dimethyl-1-indenyl, 4,7-dimethoxy-1-indenyl, fluorenyl.

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, [ ([Eta] &lt; 5 &gt; -indenyl) -dimethylsilane] titanium dichloride, [(Nt- butylamide) (eta 5 -indenyl) -dimethylsilane] titanium dichloride, [ Methylsilane] titanium dichloride.

Also exemplified are compounds wherein the "dichloride" moiety of the half-titanocene compound listed above is replaced with a compound of the following list: -dibromo, -diiodide, -dimethyl, -diethyl, -di (N, N-dimethylamino) benzyl, 2-butene-1,4-diyl, -s-trans-isoindol- -1,4-diphenyl-1,3-butadiene, -s-trans-eta4-3-methyl-1,3-pentadiene, -s- -S-trans-eta4-2,4-hexadiene, -s-trans-eta4-1,3-pentadiene, -s-trans-eta4-1,4-ditolyl-1,3-butadiene -s-trans-η4-1,4-bis (trimethylsilyl) -1,3-butadiene, -s-cis-η4-1,4-diphenyl-1,3-butadiene, -3-methyl-1,3-pentadiene, -s-cis-? 4-1,4-dibenzyl-1,3-butadiene, -s- cis-? 4-2,4-hexadiene, cis-? - 1,4-ditolyl-1,3-butadiene, -s-cis-? 4-1,4-bis (trimethylsilyl) -1,3 - Other diene.

The titanocene compound and the half titanocene compound may be used alone or in combination. Also, the titanocene compound and the half titanocene compound may be used by reacting with the organoaluminum, organolithium, and organomagnesium.

Examples of the organoaluminum which can be used by reacting with the titanocene compound and 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 and 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, A hydrocarbon group consisting of an allyloxy group, an arylamide group, an alkylallyl group having 7 to 20 carbon atoms, an alkylallyloxy group, an alkylallylamide group, an arylalkoxy group, an arylalkylamide group or an alkenyl group having 2 to 20 carbon atoms And 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 Examples of the lithium salt include lithium, diethylamide lithium, diisopropylamide lithium, dibutylamide lithium, diphenylamide lithium, phenyllithium, m-tolylithium, p-tolylithium, xylylithium, methoxyphenyllithium, There may be mentioned the quality and lithium.

Examples of the organomagnesium which can be used by reacting with the titanocene compound and the half titanocene compound include dialkylmagnesium and alkylmagnesium halide. Specific examples thereof include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, diisobutyl Examples of the solvent include magnesium, dihexyl magnesium, dioctyl magnesium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, , Allyl magnesium bromide, allyl magnesium chloride, and the like.

The amount of the titanocene compound and the half titanocene compound used in the preparation of the metallocene catalyst ranges from 35: 1 to 2: 1 in terms of the molar ratio of the metallocene compound: titanocene compound or the half titanocene compound. If the use ratio of the titanocene compound or the half titanocene compound is less than 35: 1, it is difficult to obtain the effect of increasing the molecular weight sufficiently. If the ratio is more than 2: 1, the polymerization activity is greatly decreased and the molecular weight becomes too large.

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 high molecular weight distribution and usually has an average molecular weight of about 800 to 1200. The aluminoxane is usually kept in a solution in toluene, and examples thereof include 10% or 30% methyl aluminoxane .

When the step (1) is carried out by the carrying process (a), the concentration of the aluminoxane in the solution obtained by dissolving the metallocene compound in the solution of the aluminoxane is 5 to 30% by weight, The concentration of the component is preferably 0.001 to 1.0% by weight, calculated as the metal element (M). When the concentration of each component is out of the above range, the catalytic activity is too low or too high.

The solution may comprise an aromatic hydrocarbon, aliphatic hydrocarbon or aliphatic cyclic hydrocarbon as a solvent.

In the method for producing the metallocene catalyst for use in the production of the ethylenic copolymer according to the present invention, the carrier used in the step (1) may be a solid, particulate, porous, preferably an inorganic material such as silicon And / or aluminum oxide, most preferably in the form of spherical particles, for example particles obtained by the spray-drying process, with OH groups or other functional groups containing active hydrogen atoms being most preferred.

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 and more preferably 0.7 to 1.6 mmole / g per 1 g of the silica, 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.

The carrier slurry used in the step (1) is prepared by suspending a carrier in a hydrocarbon solvent or a hydrocarbon solvent mixture.

The temperature of the carrying process in the step (1) is preferably from 40 to 160 ° C, more preferably from 80 to 120 ° C. When the temperature is out of the range, the activity decreases and polymer aggregation occurs in the reactor And the supporting time is preferably from 30 minutes to 4 hours, more preferably from 1 to 2 hours. If the temperature is out of the above-mentioned range, economical efficiency is insufficient or the reaction is insufficient, not.

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.

[Gas Phase Polymerization]

The ethylenic copolymer according to the present invention can be produced by reacting a gas phase polymerization composition comprising hydrogen, ethylene and, if necessary, a comonomer, in the presence of a metallocene supported catalyst prepared as described above as a main catalyst .

Examples of the comonomer include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, Alpha-olefins other than ethylene, which are selected from the group consisting of -tetradecene, 1-hexadecene and 1-aidocene, are preferred.

The content ratio of the comonomer and 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, it is not preferable since a desired level of copolymer can not be obtained.

In the preparation of the ethylenic copolymer of the present invention, the metallocene catalyst is preferably 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 production of the ethylenic copolymer of the present invention, 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 , Preferably 2 to 40 atm, and more preferably 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 used as the main catalyst in the production of the ethylenic copolymer 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 are trialkylaluminums having alkyl groups with 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.

The ethylenic copolymer produced by the gas phase polymerization according to the present invention contains a long chain branch in the main chain, thereby providing a high melt strength and a low processing load as compared with a general metallocene resin.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a plotting method for calculation of a complex elastic modulus plot of a prepared copolymer resin. FIG.
2 is a diagram showing a dynamic test method for phase angle shift (δ) plot calculation of the produced copolymer resin.
3 is a graph showing the result of plotting the complex elastic modulus and the phase angle shift together.
4 is a diagram showing a method of obtaining a critical phase angle value.
5 is a view showing a Rheotension meter for measuring melt strength.
6 is a graph showing the complex elastic modulus and phase angle of the copolymer resins obtained in Examples and Comparative Examples.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples so that those skilled in the art can easily carry out the present invention. The following examples are only illustrative of the present invention and do not limit the scope of protection of the present invention.

[ Example  One]

Metallocene  Preparation of Supported Catalyst

5 g of dehydrated silica with a trade name of XPO-2402 (average particle size of 50 microns, surface area of 300 m 2 / g, micropore volume of 1.6 ml / g, OH concentration of 1 mmol / g) was weighed under anhydrous condition and 20 ml of toluene was used as a slurry Lt; / RTI &gt; This was injected into a 1 L reactor equipped with a stirrer and a cooling condenser. 120 ml of methylaluminoxane solution (10 wt%) was quantified in a measuring cylinder and ethylene bis (indenyl) zirconium dichloride [Et (IND) ₂ ZrCl, which is a metallocene catalyst component preliminarily quantified in 250 ml of Schlenk ₂ ) (metallocene / silica = 120 μmol / g silica) and biscyclopentadienyl titanium dichloride [Cp ₂ TiCl ₂ ] (Cp ₂ TiCl ₂ / silica = 18 μmol / g silica) were mixed at room temperature, And the solid metallocene catalyst and Cp ₂ TiCl ₂ were dissolved and reacted at the same time. While maintaining the temperature of the reactor at room temperature, the methylaluminoxane-metallocene solution was added. Then, the reaction temperature was raised to 100 캜 with stirring. At this temperature, the support reaction was allowed to proceed for 120 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 taken out. The reaction mixture was firstly washed with 100 ml of toluene at -5 ° C. 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.

Gas phase polymerization

The polymerization process was carried out in a continuous gas fluidized bed reactor. The fluidized bed consisted of polymer particles. The gas-phase feed stream of ethylene and hydrogen and monomers were introduced into the recycle gas line below the reactor bed. 1-Hexene was used as the comonomer. The flow rates of each of ethylene, hydrogen and comonomers were adjusted to maintain the desired constant composition. The ethylene concentration was adjusted to maintain a constant ethylene partial pressure. Hydrogen was adjusted to maintain a constant hydrogen to ethylene molar ratio. The concentration of all gases was measured by an on-line gas chromatograph such that the composition of the recycle gas stream was relatively constant. The reaction bed consisting of the polymer particles was kept fluidized by the continuous flow of the supplemental feed and the recirculating gas through the reaction zone. The reactor was operated at a total pressure of 19.2 Kgf / cm ² . The reaction was initiated by injecting the metallocene supported catalyst prepared above at a constant rate. Tri-n-octylaluminum, an alkyl aluminum compound, was diluted with hexane as an activating agent for initiating the reaction at the same time as the catalyst was injected. Respectively. In order to stabilize the reaction, antistatic agent AS990 was diluted in oil and injected so as to keep the content of 25 ppm in the BED. As the polymerization progresses, the temperature of the recirculating gas is continuously increased or decreased while the recirculating gas passes through the heat exchanger so as to regulate the change in the exothermic rate caused by polymerization in order to maintain a constant reactor temperature. The fluidized bed was maintained at a constant height by withdrawing a portion of the bed at the same rate as the product formation rate. Specific gas phase polymerization conditions for the production of the ethylene copolymer are shown in Table 1 below.

Reaction conditions Temperature (℃) 80 Pressure (kgf / cm ² ) 19.2 Ethylene, mol% 35 Hydrogen, mol% 0.0065 Hydrogen / ethylene (injection rate) 0.018 Comonomer, mol% 0.35 Comonomer / ethylene (injection rate) 0.08 Bed weight (Kg) 70 Time of stay (hours) 14 Production rate (Kg / hour) 5

The physical properties of the produced ethylenic copolymer were measured by the following methods.

How to measure property

(1) Melt flow Index

The melt index was measured at 230 DEG C and 2.16 kg under the conditions of ASTM D1238.

(2) Density

The density was measured by a density gradient column according to ASTM D1505 method.

(3) Melt flow rate ratio (MFRR)

The MFRR was calculated as the ratio of the melt index (MI ₂₁ / MI ₂ ) under the load of 21.6 kg (MI ₂₁ ) and 2.16 kg (MI ₂ ) at 190 ° C.

(4) Molecular weight distribution

The molecular weight distribution was calculated as the ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) measured from GPC (Gel Permeation Chromatography).

(5) Zero Shear Viscosity: Calculated by measuring dynamic fluidity data using a frequency sweep method at 190 ° C using a Rheometric ARES flow meter. The spacing in the parallel plate structure is 2 mm, the plate diameter is 25 mm, and the deformation amplitude is 10%. The frequency was measured in the range of 0.05 to 300 rad / sec. Zero shear viscosity was calculated using the Carraeu Model.

(6) Total point viscosity ratio (SHI): Calculated from the ratio of the complex viscosity at a frequency of 0.1 rad / sec and the complex viscosity at a frequency of 100 rad / sec measured from ARES.

(7) Critical Phase Angle (? C)

First, dynamic fluidity data is measured by a frequency sweep method using TA Instruments' ARES equipment. A plot of the phase angle shift (δ) and the complex modulus (G *) from the measured data shows that the linear structure PE and the LCB structure PE have different behaviors and the LCB structure The PE of the phase angle? And the complex elastic modulus (G *) generates an inflection point at which the slope of the graph changes, which is referred to as a critical phase angle value? _C. Generally, it is known that the critical phase angle value (δ _C ) is correlated with the content of LCB, and δ _C is lower as the content of LCB is higher. The calculation method of the critical phase angle value? C is calculated from the dynamic fluidity data measured as follows.

① Complex modulus plot calculation

G * is calculated from the results of G '(storage modulus) and G' (loss modulus) using the following equation (1), and plotted as shown in FIG.

......①

...... ①

Here, G '= (σ ₀ / γ ₀ ) cos δ, G "= (σ ₀ / γ ₀ ) sin δ

② Phase angle shift (δ) plot calculation

The dynamic test method using the ARES of the strain control type applies the oscillation strain to the molten polymer as a sinusoidal function as shown in FIG. 2, measures the stress at that time, The method of measuring the correlation between stress and strain shows viscoelasticity in combination of elastic in-phase characteristics and viscous out-of-phase. The G * (complex modulus) obtained above is plotted as a phase angle shift (?) To obtain the result shown in FIG. FIG. 3 is a plot of the linear structure PE and the LCB structure PE, which shows the difference depending on the structure.

③ Calculate the critical phase angle value (δ _C )

The inflection point at which the slope of the graph changes in the complex elastic modulus (G *) versus phase angle (?) Curve becomes the critical phase angle? _C value. As shown in FIG. 4, a slope is determined by designating a section that is a straight line from the lower G * value. After passing the inflection point again, specify the straight line to obtain the slope. The slope of the two sections is obtained and the critical phase angle (δ _C ) is obtained at the intersection.

(8) Melt strength

The melt strength of each sample was measured using a Rheotension meter as shown in FIG. The molten resin passed through the orifice by constant force was pulled off at an increased speed and the stress applied to it was measured by a load cell. As the pulling speed increases, the melt tension increases but remains at a constant value, which is defined as the melt tension value of the measuring resin. The temperature of the melting pot is 150 占 폚, and the temperature of the chamber is 90 占 폚. The orifice diameter is 2 mm, the L / D 32/2, the resin inlet angle is 30 °, and the piston speed is 10 mm / min.

(9) Haze (%)

The haze value (%) of the molded film was measured according to ASTM D-1003-95.

[ Example  2]

Metallocene  Preparation of Supported Catalyst

(IND) ₂ ZrCl ₂ ] (metallocene / silica = 120 μmol / g silica) and biscyclopentadienyl (indenyl) zirconium dichloride in the preparation of the metallocene supported catalyst of Example 1 (Indenyl) zirconium dichloride [Et (IND) ₂ ZrCl ₂ ] (metallocene / silica = 60 μmol) instead of titanium dichloride [Cp ₂ TiCl ₂ ] (Cp ₂ TiCl ₂ / silica = 18 μmol / g silica) / g silica) and ethylene bis (4,5,6,7-tetrahydridoindenyl) zirconium dichloride [Et (THI) ₂ ZrCl ₂ ] (metallocene / silica = 35 μmol / g silica) A catalyst was prepared in the same manner as in Example 1, except that the cyclopentadienyl titanium dichloride [Cp ₂ TiCl ₂ ] (Cp ₂ TiCl ₂ / silica = 18 μmol / g silica) was used.

Gas phase polymerization

Except that the hydrogen / ethylene molar ratio was adjusted to 0.02 and the 1-hexene / ethylene molar ratio was adjusted to 0.1 to adjust the composition of the comonomer (1-hexene) gas phase in order to control the hydrogen gas phase composition in the gas phase polymerization process of Example 1 , Vapor phase polymerization was carried out in the same manner as in Example 1 to obtain an ethylene copolymer.

[ Example  3]

Synthesis of dimethylsilylene (t- butylamido ) -tetramethylcyclopentadienyl ) titanium dibenzyl [(Me ₂ Si (NtBu) (Cp *) Ti (Bn) ₂ ]

5.2 mmol of Ti (CH ₂ Ph) ₄ and _4.0 mmol of dimethylsilylene (t-butylamido) (tetramethylcyclopentadienyl) were weighed, and 50 mL of toluene purified by Schlenk Line dissolved. raise the temperature of the sun is blocked the reactor at 60 ℃, the reaction was carried out for 12 hours the reaction was dried under vacuum. the dried reaction product was again extracted with pentane, which was further dried in vacuo and finally Me ₂ Si (NtBu) (Cp *) Ti (Bn) 2 was obtained. the yield was> was 90%. the structure of the resulting final compound was confirmed by ¹ H NMR.

^{1 H NMR (400MHz, C6D6)} 7.16 (Ph, 4H, d), 6.95 (Ph, 4H, t), 6.90 (Ph, 2H, t), 2.58 (CH 2 Ph, 2H, d), 2.25 (CH 2 Ph, 2H, d), 1.81 (C 5 Me 4, 6H, s), 1.63 (C 5 Me 4, 6H, s), 1.43 (tNBu, 9H, s), 0.41 (SiMe 2, 6H, s)

Metallocene  Preparation of Supported Catalyst

(IND) ₂ ZrCl ₂ ] (metallocene / silica = 120 μmol / g silica) and biscyclopentadienyl (indenyl) zirconium dichloride in the preparation of the metallocene supported catalyst of Example 1 Ethylene bis (indenyl) zirconium dichloride [Et (IND) ₂ ZrCl ₂ ] (metallocene / silica = 35 μmol) instead of titanium dichloride [Cp ₂ TiCl ₂ ] (Cp ₂ TiCl ₂ / silica = 18 μmol / g silica) / g silica) and dimethylsilylene (t-butylamido) -tetramethylcyclopentadienyl) titanium dibenzyl [Me ₂ Si (NtBu) (Cp *) Ti (Bn) ₂ ] The same procedure as in Example 1 was carried out except that biscyclopentadienyl titanium dichloride [Cp ₂ TiCl ₂ ] (Cp ₂ TiCl ₂ / silica = 18 μmol / g silica) was used instead of biscyclopentadienyl titanium dichloride To prepare a catalyst.

Gas phase polymerization

Except that the hydrogen / ethylene molar ratio was adjusted to 0.016 and the 1-hexene / ethylene molar ratio was adjusted to 0.08 to adjust the composition of the comonomer (1-hexene) gas phase in the gas phase polymerization process of Example 1 to control the hydrogen gas phase composition , Vapor phase polymerization was carried out in the same manner as in Example 1 to obtain an ethylene copolymer.

[ Comparative Example  One]

An ethylene copolymer was obtained by gas phase polymerization in the same manner as in Example 1, except that 1018CA of Exxonmobil, which is commercially available as a metallocene catalyst, was used.

[ Comparative Example  2]

An ethylene copolymer was obtained by gas phase polymerization in the same manner as in Example 1, except that 7120S of Samsung Total sold as a metallocene catalyst was used.

[ Comparative Example  3]

An ethylene copolymer was obtained by gas phase polymerization in the same manner as in Example 1, except that 4220S of Samsung Total sold commercially as a metallocene catalyst was used and 1-butene was used instead of 1-hexene as a comonomer.

The physical properties of the copolymer resins obtained in the above Examples and Comparative Examples are measured and summarized in Table 2 below. A graph of the complex elastic modulus and phase angle of each resin is shown in FIG.

 [Table 2]

As shown in Table 2 and FIG. 6, it can be seen that the LCB characteristic inflection point is formed according to the metallocene catalysts as in Examples 1 to 3, and the critical phase angle value is shown. And shows a higher melt strength as compared with the metallocene catalyst-based resin and Ziegler-Natta type resin of the comparative example having the same molecular weight (MI = 1).

Blow  Production of film

Using the copolymer resin of Example 2 with MI = 1 and the copolymer resin of Comparative Examples 1 to 3 among the above examples, film formation was carried out under the following conditions, and the workability and physical properties of the produced films were measured .

A blown film having a film thickness of 50 占 퐉 at a working temperature of 190 占 폚 and a screw rotation speed of 50 rpm and BUR2 was produced by using a blown film molding machine having a 50 mm? Screw, a die diameter of 100 mm and a die gap of 2.5 mm.

Table 3 shows the results of measurement of workability and physical properties of the produced films.

[Table 3]

As can be seen from the above Table 3, the resin of Example 2 exhibited the lowest load during extrusion processing, showed the highest processing load and bubble instability in the case of the resin of Comparative Example 1 which did not exhibit the inflection point at the phase angle, The bubble was stable but the processing load was higher than that of the Ziggler type resin. In the case of Comparative Example 3 which is a Ziegler-type resin, the bubbles were stable and the processing load was relatively low due to the broad molecular weight distribution characteristics even without the LCB characteristic, but the haze was very high and the mechanical properties were low. In Example 2, the extrusion processing characteristics were remarkably improved compared to the conventional metallocene resin without a sharp decrease in the mechanical properties of the film.

Claims (8)

An ethylene-based copolymer produced by copolymerizing ethylene with an alpha-olefin using a metallocene catalyst and having the following characteristics:
1) a melt flow index of 0.1 to 15.0 g / 10 min (190 캜, 2.16 Kg load)
2) a density of 0.900 to 0.929 g / mL,
3) a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.5 to 6.0,
4) In the correlation between the complex elastic modulus measured by the dynamic shear viscometer and the phase angle, the correlation curve between the phase angle and the complex elastic modulus has an inflection point between the complex elastic modulus values of 10 ³ to 10 ⁷ and the critical phase angle value ? c) is 20 to 70,
The metallocene catalyst is prepared by a process comprising the steps of:
(1) a step of supporting aluminoxane, a metallocene compound and a titanocene compound or a half titanocene compound on a carrier, wherein the use ratio of the metallocene compound: titanocene compound or the half titanocene compound is 35: 1 to 2: 1;
(2) washing the supported catalyst obtained in the step (1) with an organic solvent; And
(3) drying the washed catalyst of step (2) and recovering it as a catalyst powder,
The metallocene compound is composed of at least one selected from the compounds represented by the following general formulas (1) to (3)
(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, q is 1? q? 4;
Q (CpR _n ) (CpR ' _m ) ML _q (2)
Here, Cp, R, R ', M and L have the same meanings as in the general formula (1)
Q is a bridge bond between Cp rings and represents a dialkyl, alkylaryl, 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, q is 1? q? 4;

(3)
(C ₅ H _{5 -yx} R _x ) represents the number of substituents attached to the cyclopentadienyl, x is 0, 1, 2, 3 or 4, 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,
Y 'represents -O-, -S-, -NR * -, or -PR * - wherein R * represents hydrogen, a hydrocarbon group of 1 to 12 carbon atoms, a hydrocarbyloxy group of 1 to 8 carbon atoms, A halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a multifunctional group thereof)
Z represents SiR * ₂ , CR * ₂ , SiR * ₂ SiR * ₂ , CR * ₂ CR * ₂ , CR * = CR *, CR * ₂ SiR * ₂ or GeR * ₂ , The same,
Each L independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, 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 hydrocarbon group having 1 to 18 carbon atoms A hydrocarbylsulfide group having 1 to 18 carbon atoms, a hydrocarbylsulfide group having 1 to 18 carbon atoms, and a multifunctional group thereof,
M represents a transition metal of group 4 or group 5 of the periodic table. The process of claim 1 wherein said alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-tetradecene, 1-hexadecene, and 1-aidocene. delete delete The ethylenic copolymer according to claim 1, wherein the titanocene compound or the half titanocene compound is selected from compounds represented by the following formula (4):
(CpRn) (CpR'm) TiLq (4)
Wherein Cp is cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl,
Rn and R'm each independently represent hydrogen, a hydrocarbon 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, q is 1? q? The ethylenic copolymer according to claim 1, wherein the ethylenic copolymer is produced in a gas phase polymerization reactor. The ethylene copolymer according to claim 1, wherein the ethylenic copolymer has a ratio (MI ₂₁ / MI ₂ ) of a melt index (MI ₂₁ ) measured at 190 ° C and 21.6 kg and a melt index (MI ₂ ) measured at 190 ° C and 2.16 kg, Is in the range of 15 to 100. The ethylene- The ethylenic copolymer according to claim 1, wherein the content of the alpha-olefin in the copolymer is 1 to 20% by weight.

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