Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst

Abstract

Metallocene compounds of the invention are useful as olefin polymerization catalysts or catalyst components. Olefin polymerization processes of the invention involve an olefin polymerization catalyst containing the metallocene compound. In detail, the olefin polymerization catalysts can catalyze with high polymerization activity the production of olefin polymers having high melt tension, excellent mechanical strength and good particle properties, and the olefin polymerization processes involve the catalysts. Ethylene polymers according to the invention are obtained by the polymerization processes and have higher processability and easy-opening properties and particularly excellent mechanical strength compared to conventional ethylene polymers. Thermoplastic resin compositions of the invention contain the ethylene polymers. In more detail, shaped articles or films are obtained from the ethylene polymers or the thermoplastic resin compositions containing the ethylene polymers, and laminate films include the films. According to the invention, a single or plural kinds of bridged metallocene compounds having differing cyclopentadienyl-derived groups afford macromonomers that are a source of long-chain branches and simultaneously catalyze the repolymerization of the macromonomers into olefin polymers having a large number of long-chain branches, small neck-in in the T-die extrusion, small take-up surge and superior mechanical strength. The olefin polymerization catalysts and the polymerization processes can efficiently produce the olefin polymers.

1 . A bridged metallocene compound represented by Formula [1] below: 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3  and R 4  are selected from a hydrogen atom, hydrocarbon groups, silicon-containing groups, heteroatom-containing groups and halogen-containing groups and are the same or different from one another; R 1 , R 2 , R 3  and R 4  are not all hydrogen atoms and at least one of these groups is an ethyl group or a group represented by any of Formulae [2] to [7] below; neighboring substituent groups among R 1  to R 4  may be linked together to form an aliphatic ring; Q 1  is selected from C1-20 hydrocarbon groups, halogen-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups; X independently at each occurrence is a group selected from a hydrogen atom, halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups and phosphorus-containing groups; and M is a titanium atom, a zirconium atom or a hafnium atom; 
       
       
         
           
           
               
               
           
         
         wherein R 7  to R 16  are selected from a hydrogen atom, hydrocarbon groups, silicon-containing groups, heteroatom-containing groups and halogen-containing groups and are the same or different from one another, but they are not aryl groups; D and E are each a divalent heteroatom; G and L are each a trivalent heteroatom; and T and W are each a tetravalent heteroatom or a carbon atom. 
       
     
     
         2 . An olefin polymerization catalyst (a) comprising the following components (A) and (C):
 Component (A): the bridged metallocene compound of Formula [1] described in  claim 1 ;   Component (C): at least one compound selected from the group consisting of:
 (c-1) organometallic compounds represented by Formulae [11], [12] and [13] below; 
 (c-2) organoaluminum oxy-compounds; and 
 (c-3) compounds that react with the component (A) to form an ion pair;
   R a   m Al(OR b ) n H p X q   [11] 
 
   wherein R a  and R b  are each a C1-15 hydrocarbon group and are the same or different from each other; X is a halogen atom; 0<m≦3, 0≦n<3, 0≦p<3, 0≦q<3 and m+n+p+q=3;
   M a AlR a   4   [12] 
   wherein M a  is Li, Na or K; and R a  is a C1-15 hydrocarbon group;
   R a   r M b R b   s X t   [13] 
   wherein R a  and R b  are each a C1-15 hydrocarbon group and are the same or different from each other; M b  is selected from Mg, Zn and Cd; X is a halogen atom; 0<r≦2, 0≦s≦1, 0≦t≦1 and r+s+t=2.   
     
     
         3 . An olefin polymerization catalyst (b) comprising the following components (A), (B) and (C):
 Component (A): the bridged metallocene compound of Formula (1) described in  claim 1 ;   Component (B): a bridged metallocene compound represented by Formula [14] below;   
       
         
           
           
               
               
           
         
         wherein R 17  to R 20 , and R 21  to R 28  are selected from a hydrogen atom, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups and are the same or different from one another; neighboring substituent groups among these groups may be linked together to form a ring; Q 2  is selected from C1-20 hydrocarbon groups, halogen-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups; M is selected from a titanium atom, a zirconium atom and a hafnium atom; and X independently at each occurrence is a group selected from a hydrogen atom, halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups and phosphorus-containing groups; 
         Component (C): at least one compound selected from the group consisting of: 
         (c-1) organometallic compounds represented by Formulae [18], [19] and [20] below; 
         (c-2) organoaluminum oxy-compounds; and 
         (c-4) compounds that react with the components (A) and (B) to form an ion pair;
   R a   m Al(OR b ) n H p X q   [18] 
 
         wherein R a  and R b  are each a C1-15 hydrocarbon group and are the same or different from each other; X is a halogen atom; 0<m≦3, 0≦n<3, 0≦p<3, 0≦q<3 and m+n+p+q=3;
   M a AlR a   4   [19] 
 
         wherein M a  is Li, Na or K; and R a  is a C1-15 hydrocarbon group;
   R a   r M b R b   s X t   [20] 
 
         wherein R a  and R b  are each a C1-15 hydrocarbon group and are the same or different from each other; M b  is selected from Mg, Zn and Cd; X is a halogen atom; 0<r≦2, 0≦s≦1, 0≦t≦1 and r+s+t=2. 
       
     
     
         4 . The olefin polymerization catalyst (b) according to  claim 3 , which comprises a solid catalyst component (K1) comprising a solid carrier (S), the component (C) and the component (A), and a solid catalyst component (K2) comprising a solid carrier (S), the component (C) and the component (B). 
     
     
         5 . The olefin polymerization catalyst (b) according to  claim 3 , which comprises a solid catalyst component (K3) comprising a solid carrier (S), the component (A), the component (B) and the component (C). 
     
     
         6 . The olefin polymerization catalyst (b) according to any one of  claims 3  to  5 , wherein in Formula [1], at least one of R 1 , R 2 , R 3  and R 4  is a hydrocarbon group. 
     
     
         7 . The olefin polymerization catalyst (b) according to any one of  claims 3  to  5 , wherein the component (C) is an organoaluminum oxy-compound (c-2). 
     
     
         8 . The olefin polymerization catalyst (b) according to any one of  claims 4  to  7 , wherein the solid carrier (S) is a porous oxide. 
     
     
         9 . A process for producing olefin polymers, comprising polymerizing one or more monomers selected from ethylene and C3-20 olefins in the presence of the olefin polymerization catalyst described in any one of  claims 2  to  8 , wherein at least one of the monomers is ethylene or propylene. 
     
     
         10 . A process for producing ethylene polymers, Comprising homopolymerizing ethylene or copolymerizing ethylene and a C3-20 olefin in the presence of the olefin polymerization catalyst described in any one of  claims 2  to  8 . 
     
     
         11 . An ethylene polymer (i) which is obtained by homopolymerizing ethylene or polymerizing ethylene and a C4-20 olefin in the presence of the olefin polymerization catalyst described in any one of  claims 3  to  8  and which satisfies the following requirements [1] to [5] at the same time:
 [1] the melt flow rate (MFR) as measured at 190° C. under a load of 2.16 kg is in the range of 0.1 to 100 g/10 min;   [2] the density (d) is in the range of 875 to 970 kg/m 3 ;   [3] the ratio [MT/η*(g/P)] is in the range of 1.50×10 −4  to 9.00×10 −4  wherein [MT(g)] is the melt tension at 190° C. and [η*(P)] is the shear viscosity at 200° C. and an angular velocity of 1.0 rad/sec;   [4] per 1000 carbon atoms, the total of methyl branches [A(/1000 C)] and ethyl branches [B(/1000 C)], [(A+B)(/1000 C)], is not more than 1.8 according to  13 C-NMR;   [5] the zero-shear viscosity at 200° C. [η 0 (P)] and the weight average molecular weight (Mw) measured by GPC-viscometry (GPC-VISCO) satisfy Equation (Eq-1) below:
   0.01×10 −13 ×Mw 3.4 ≦η 0 ≦4.5×10 −13 ×Mw 3.4   (Eq-1) 
   
     
     
         12 . An ethylene polymer (ii) which is obtained by homopolymerizing ethylene or polymerizing ethylene and a C4-20 olefin in the presence of the olefin polymerization catalyst described in any one of  claims 3  to  8  and which satisfies the following requirements [1] to [6] at the same time:
 [1] the melt flow rate (MFR) as measured at 190° C. under a load of 2.16 kg is in the range of 0.1 to 100 g/10 min;   [2] the density (d) is in the range of 875 to 970 kg/m 3 ;   [3] the ratio [MT/η*(g/P)] is in the range of 2.50×10 −4  to 9.00×10 −4  wherein [MT(g)] is the melt tension at 190° C. and [η*(P)] is the shear viscosity at 200° C. and an angular velocity of 1.0 rad/sec;   [4] per 1000 carbon atoms, the total of methyl branches [A(/1000 C)] and ethyl branches [B(/1000 C)], [(A+B)(/1000 C)], is not more than 1.8 according to  13 C-NMR;   [5] the zero-shear viscosity at 200° C. [η 0 (P)] and the weight average molecular weight (Mw) measured by GPC-viscometry (GPC-VISCO) satisfy Equation (Eq-1) below:
   0.01×10 −13 ×Mw 3.4 ≦η 0 ≦4.50×10 −13 ×Mw 3.4   (Eq-1) 
   [6] a molecular weight distribution curve obtained by GPC shows a molecular weight at a maximum weight fraction (peak top M) in the range of 1.0×10 4.30  to 1.0×10 4.50 .   
     
     
         13 . An ethylene polymer (iii) which is obtained by homopolymerizing ethylene or polymerizing ethylene and a C4-20 olefin in the presence of the olefin polymerization catalyst described in any one of  claims 3  to  8  and which satisfies the following requirements [1] to [6] at the same time:
 [1] the melt flow rate (MFR) as measured at 190° C. under a load of 2.16 kg is in the range of 0.1 to 100 g/10 min;   [2] the density (d) is in the range of 875 to 936 kg/m 3 ;   [3] the ratio [MT/η*(g/P)] is in the range of 2.50×10 −4  to 9.00×10 −4  wherein [MT(g)] is the melt tension at 190° C. and [η*(P)] is the shear viscosity at 200° C. and an angular velocity of 1.0 rad/sec;   [4] per 1000 carbon atoms, the total of methyl branches [A(/1000 C)] and ethyl branches [B(/1000 C)], [(A+B)(/1000 C)], is not more than 1.8 according to  13 C-NMR;   [5] the zero-shear viscosity at 200° C. [η 0 (P)] and the weight average molecular weight (Mw) measured by GPC-viscometry (GPC-VISCO) satisfy Equation (Eq-1) below:
   0.01×10 −13 ×Mw 3.4 ≦η 0 ≦4.50×10 −13 ×Mw 3.4   (Eq-1) 
   [6] a molecular weight distribution curve obtained by GPC shows a molecular weight at a maximum weight fraction (peak top M) in the range of 1.0×10 4.20  to 1.0×10 4.50 .   
     
     
         14 . An ethylene polymer (iv) which is obtained by polymerizing ethylene and a C3-20 olefin in the presence of the olefin polymerization catalyst described in any one of  claims 3  to  8  and which satisfies the following requirements [1] to [5] at the same time:
 [1] the ratio [M 3-4 /M 3-10 ] is in the range of 0.30 to 1.00 wherein [M 3-4  (mol %)] is the content of C3-4 α-olefins and [M 3-10  (mol %)] is the content of C3-10 α-olefins according to  13 C-NMR;   [2] the melt flow rate (MFR) as measured at 190° C. under a load of 2.16 kg is in the range of 0.1 to 100 g/10 min;   [3] the density (d) is in the range of 875 to 970 kg/m 3 ;   [4] the ratio [MT/η*(g/P)] is in the range of 1.50×10 −4  to 9.00×10 −4  wherein [MT(g)] is the melt tension at 190° C. and [η*(P)] is the shear viscosity at 200° C. and an angular velocity of 1.0 rad/sec;   [5] the zero-shear viscosity at 200° C. [η 0 (P)] and the weight average molecular weight (Mw) measured by GPC-viscometry (GPC-VISCO) satisfy Equation (Eq-1) below:
   0.01×10 −13 ×Mw 3.4 ≦η 0 ≦4.50×10 −13 ×Mw 3.4   (Eq-1) 
   
     
     
         15 . A shaped article obtained from the ethylene polymer described in any one of  claims 9  to  14 . 
     
     
         16 . The shaped article according to  claim 15 , which is a film.