Catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene-based copolymer, propylene polymer, propylene-based polymer composition, and use of those

Abstract

A catalyst for olefin polymerization, comprising: (A-1) a bridged metallocene compound represented by the following Formula [1-1], and (b) at least one compound selected from: (b-1) an organoaluminum oxy compound, (b-2) a compound which forms an ion pair, and (b-3) an organoaluminum compound: wherein in Formula [1-1], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , and R 12 are each selected from a hydrogen, a hydrocarbon group and a silicon-containing group; the four groups of R 6 , R 7 , R 10 , and R 11 are not hydrogen atoms, and are each selected from a hydrocarbon group or a silicon-containing group; R 13 and R 14 are each a hydrocarbon group or the like, excluding a hydrogen atom and a methyl group; M is Ti, Zr or the like; Y is carbon or the like; Q is a halogen or the like; and j is an integer from 1 to 4.

1 . A propylene-based polymer composition (X1) comprising:
 10 to 95 parts by weight of a syndiotactic propylene polymer (AA) and   90 to 5 parts by weight of a propylene.α-olefin copolymer (B2) (provided that the sum of amounts of (AA) and (B2) is 100 parts by weight),   wherein the polymer (AA) satisfies the following requirement (a), and the copolymer (B2) satisfies the following requirement (b):   (a) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as determined by DSC is 145° C. or higher, and constituent units derived from propylene is contained in an amount of more than 90 mol % (provided that the total amount of the constituent units in the polymer (AA) is 100 mol %);   (b) constituent units derived from propylene is contained in an amount of 55 to 90 mol %, constituent units derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) is contained in an amount of 10 to 45 mol % (provided that the sum of amounts of the constituent units derived from propylene and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol %), the MFR measured according to JIS K-6721 at 230° C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one of the following requirements (b-1) and (b-2) is satisfied;   (b-1) the syndiotactic triad fraction (rr fraction) as measured by  13 C-NMR is 60% or greater; and   (b-2) the intrinsic viscosity [η] (dL/g) as measured in decalin at 135° C. and the MFR (g/10 min, 230° C., under a load of 2.16 kg) satisfy the following relationship:
   1.50× MFR   (−0.20) ≦[η]≦2.65× MFR   (−0.20) .
 
   
     
     
         2 . The propylene-based polymer composition (X1) according to  claim 1 , which comprises:
 50 parts by weight or more and 95 parts by weight or less of the syndiotactic propylene polymer (AA), and   5 parts by weight or more and 50 parts by weight or less of the propylene.α-olefin copolymer (B2) (the sum of amounts of (AA) and (B2) is 100 parts by weight).   
     
     
         3 . The propylene-based polymer composition (X1) according to  claim 1 , which comprises:
 10 parts by weight or more and less than 50 parts by weight of the syndiotactic propylene polymer (AA), and   more than 50 parts by weight and 90 parts by weight or less of the propylene.α-olefin copolymer (B2) (the sum of amounts of (AA) and (B2) is 100 parts by weight).   
     
     
         4 . The propylene-based polymer composition (X1) according to  claim 1 , which has (1) a half-crystallization time (t 1/2 ) during isothermal crystallization at 110° C. as determined by differential scanning calorimetry in the range of 1,000 sec or less. 
     
     
         5 . The propylene-based polymer composition (X1) according to  claim 1 , which has (2) a needle penetration temperature of 145° C. or higher. 
     
     
         6 . The propylene-based polymer composition (X1) according to  claim 2 , which has:
 (2) a needle penetration temperature of 145° C. or higher,   (3) an Izod impact strength at 0° C. of 50 J/m or larger,   (4) a tensile modulus in the range of 100 MPa to 2,000 MPa, and   (5) an internal haze value of a press sheet having a thickness of 1 mm of 50% or less.   
     
     
         7 . The propylene-based polymer composition (X1) according to  claim 3 , which has:
 (2) a needle penetration temperature of 145° C. or higher,   (4) a tensile modulus in the range of 1 MPa to 400 MPa, and   (5) an internal haze value of a press sheet having a thickness of 1 mm of 30% or less.   
     
     
         8 . The propylene-based polymer composition (X1) according to  claim 1 , wherein the syndiotactic propylene polymer (AA) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.1 to 10 dL/g, and a heat of fusion (ΔH) determined by differential scanning calorimetry (DSC) of 40 mJ/mg or greater. 
     
     
         9 . The propylene-based polymer composition (X1) according to  claim 1 , wherein the propylene.α-olefin polymer (B2) has a molecular weight distribution (Mw/Mn, Mn: number average molecular weight, Mw: weight average molecular weight) as determined by GPC, of 3.5 or less. 
     
     
         10 . Pellets comprising a propylene-based polymer composition (W), said composition (W) comprising:
 1 to 65 parts by weight of a syndiotactic propylene polymer (AA1), and   99 to 35 parts by weight of a propylene.α-olefin copolymer (B21) (provided that the sum of amounts of (AA1) and (B21) is 100 parts by weight),   wherein the polymer (AA1) satisfies the following requirement (a1), and the copolymer (B21) satisfies the following requirement (b1):   (a1) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as determined by DSC is 145° C. or higher, and constituent units derived from propylene are contained in an amount of more than 90 mol % (provided that the total amount of the constituent units in the polymer (AA1) is 100 mol %),   (b1) constituent units derived from propylene are contained in an amount of 55 to 90 mol %, constituent units derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are contained in an amount of 10 to 45 mol % (provided that the sum of amounts of the constituent units derived from propylene and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol %), the MFR measured according to JIS K-6721 at 230° C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one of the following requirements (b1-1) and (b1-2) is satisfied:   (b1-1) the syndiotactic triad fraction (rr fraction) as measured by  13 C-NMR is 60% or greater.   (b1-2) the intrinsic viscosity [η] (dL/g) as measured in decalin at 135° C. and the MFR (g/10 min, 230° C., under a load of 2.16 kg) satisfy the following relationship:
   1.50× MFR   (−0.20) ≦[η]≦2.65× MFR   (−0.20) .
 
   
     
     
         11 . A propylene-based polymer composition (X2) comprising:
 100 to 25 parts by weight of a syndiotactic propylene polymer (AA),   0 to 75 parts by weight of a propylene.α-olefin copolymer (B2) (provided that the sum of amounts of (AA) and (B2) is 100 parts by weight), and   1 to 100 parts by weight of an ethylene.α-olefin copolymer (C0) based on 100 parts by weight of the sum of amounts of (AA) and (B2),   wherein the polymer (AA) satisfies the following requirement (a), the polymer (B2) satisfies the following requirement (b), and the copolymer (C0) satisfies the following requirement (c):   (a) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as measured by DSC is 145° C. or higher, and constituent units derived from propylene is contained in an amount of more than 90 mol % (provided that the total amount of the constituent units in the polymer (AA) is 100 mol %),   (b) constituent units derived from propylene are contained in an amount of 55 to 90 mol %, constituent units derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are contained in an amount of 10 to 45 mol % (provided that the sum of amounts of the constituent units derived from propylene and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol %), the MFR measured according to JIS K-6721 at 230° C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one of the following requirements (b-1) and (b-2) is satisfied:   (b-1) the syndiotactic triad fraction (rr fraction) as measured by  13 C-NMR is 60% or greater, and   (b-2) the intrinsic viscosity [η] (dL/g) as measured in decalin at 135° C. and the MFR (g/10 min, 230° C., under a load of 2.16 kg) satisfy the following relationship:
   1.50× MFR   (−0.20) ≦[η]≦2.65× MFR   (−0.20) ,
 
   (c) constituent units derived from ethylene are contained in an amount of 50 to 99 mol %, and constituent units derived from an α-olefin having 3 to 20 carbon atoms other than ethylene are contained in an amount of 1 to 50 mol % (provided that the sum of amounts of the constituent units derived from ethylene and the constituent units derived from the α-olefin having 3 to carbon atoms is 100 mol %).   
     
     
         12 . The propylene-based polymer composition (X2) according to  claim 11 , which comprises:
 98 to 40 parts by weight of the syndiotactic propylene polymer (AA);   2 to 60 parts by weight of the propylene.α-olefin copolymer (B2) (provided that the sum of amounts of (AA) and (B2) is 100 parts by weight); and   1 to 100 parts by weight of the ethylene.α-olefin copolymer (C0) based on 100 parts by weight of the sum of amounts of (AA) and (B2),   wherein the polymer (AA) satisfies the following requirement (a), the copolymer (B2) satisfies the following requirement (b′), and the copolymer (C0) satisfies the following requirement (c′):   (a) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as determined by DSC is 145° C. or higher, and constituent units derived from propylene is contained in an amount of more than 90 mol % (provided that the total amount of the constituent units in the polymer (AA) is 100 mol %),   (b′) constituent units derived from propylene are contained in an amount of 65 to 90 mol %, constituent units derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are contained in an amount of 10 to 35 mol % (provided that the sum of amounts of the constituent units derived from propylene and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol %), the MFR as measured according to JIS K-6721 at 230° C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one of the following requirements (b-1) and (b-2) is satisfied:   (b-1) the syndiotactic triad fraction (rr fraction) as measured by  13 C-NMR is 60% or greater, and   (b-2) the intrinsic viscosity [η] (dL/g) as measured in decalin at 135° C. and the MFR (g/10 min, 230° C., under a load of 2.16 kg) satisfy the following relationship:
   1.50× MFR   (−0.20) ≦[η]≦2.65× MFR   (−0.20) ,
 
   (c′) constituent units derived from ethylene are contained in an amount of 60 to 95 mol %, and constituent units derived from the α-olefin having 3 to 20 carbon atoms other than ethylene are contained in an amount of 5 to 40 mol % (provided that the sum of amounts of the constituent units derived from ethylene and the constituent units derived from the α-olefin having 3 to 20 carbon atoms is 100 mol %).   
     
     
         13 . The propylene-based polymer composition (X2) according to  claim 11 , which comprises:
 100 parts by weight of the syndiotactic propylene polymer (AA); and   1 to 100 parts by weight of the ethylene.α-olefin copolymer (C0),   wherein the polymer (AA) satisfies the following requirement (a), and the copolymer (C0) satisfies the following requirement (c′):   (a) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as determined by DSC is 145° C. or higher, and constituent units derived from propylene are contained in an amount of more than 90 mol % (provided that the total amount of the constituent units in the polymer (AA) is 100 mol %), and   (c′) constituent units derived from ethylene are contained in an amount of 60 to 95 mol %, and constituent units derived from the α-olefin having 3 to 20 carbon atoms other than ethylene are contained in an amount of 5 to 40 mol % (provided that the sum of amounts of the constituent units derived from ethylene and the constituent units derived from the α-olefin having 3 to 20 carbon atoms is 100 mol %).   
     
     
         14 . The propylene-based polymer composition (X2) according to  claim 11 , which has (1) a half-crystallization time (t 1/2 ) during isothermal crystallization at 110° C. as determined by differential scanning calorimetry in the range of 1,000 sec or less. 
     
     
         15 . The propylene-based polymer composition (X2) according to  claim 11 , which has (2) a needle penetration temperature of 145° C. or higher. 
     
     
         16 . The propylene-based polymer composition (X2) according to  claim 11 , wherein the syndiotactic propylene polymer (AA) has an intrinsic viscosity [η] as measured in decalin at 135° C. in the range of 0.1 to 10 dL/g, and a heat of fusion (ΔH) of 40 mJ/mg or greater. 
     
     
         17 . The propylene-based polymer composition (X2) according to  claim 11 , wherein the propylene.α-olefin polymer (B2) has a molecular weight distribution (Mw/Mn, Mn: number average molecular weight, Mw: weight average molecular weight), as measured by GPC, of 3.5 or less. 
     
     
         18 . The propylene-based polymer composition (X2) according to  claim 11 , wherein the ethylene.α-olefin copolymer (C0) has an MFR in the range of 0.01 to 100 g/10 min, as measured according to JIS K-6721 at 190° C. under a load of 2.16 kg, and a density of 0.910 to 0.850 (g/cm 3 ). 
     
     
         19 . A propylene-based polymer composition (X3), comprising:
 10 to 95 parts by weight of a syndiotactic propylene polymer (AA), and   90 to 5 parts by weight of a propylene.α-olefin copolymer (B3) (provided that the sum of amounts of (AA) and (B3) is 100 parts by weight),   wherein the polymer (AA) satisfies the following requirement (a) and the copolymer (B3) satisfies the following requirement (b):   (a) the syndiotactic pentad fraction (rrrr fraction) as measured by  13 C-NMR is 85% or greater, the melting point (Tm) as determined by DSC is 145° C. or higher, and constituent units derived from propylene are contained in an amount of more than 90 mol % (provided that the total amount of the constituent unit in the polymer (AA) is 100 mol %), and   (b) constituent units derived from propylene are contained in an amount of 30 to 90 mol %, constituent units derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms (excluding propylene) are contained in an amount of 10 to 70 mol % (provided that the sum of amounts of the constituent units derived from propylene and the constituent units derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol %), the MFR measured according to JIS K-6721 at 230° C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one of the following requirements (b-1) and (b-2) is satisfied:   (b-1) the syndiotactic triad fraction (rr fraction) as measured by  13 C-NMR is 60% or greater, and   (b-2) the intrinsic viscosity [η] (dL/g) as measured in decalin at 135° C. and the MFR (g/10 min, 230° C., under a load of 2.16 kg) satisfy the following relationship:
   1.50× MFR   (−0.20) ≦[η]≦2.65× MFR   (−0.20) .
 
   
     
     
         20 . The propylene-based polymer composition (X3) according to  claim 19 , wherein the propylene.α-olefin copolymer (B3) comprises constituent units derived from propylene in an amount of 30 to 90 mol %, and constituent units derived from ethylene and constituents unit derived from an α-olefin having 4 to 20 carbon atoms in a total amount of 10 to 70 mol % (the sum of amounts of the constituent units derived from propylene, the constituent units derived from ethylene and constituent units derived from the α-olefin having 4 to 20 carbon atoms is 100 mol %), and satisfies P E ·P HAO  when the proportion of the constituent units derived from ethylene is designated as P E  (mol %), and the proportion of the constituent units derived from the α-olefin having 4 to 20 carbon atoms is designated as P HAO  (mol %). 
     
     
         21 . The propylene-based polymer composition (X3) according to  claim 19 , further comprising 0.1 to 100 parts by weight of one or more resins (C1) selected from the group consisting of rosin-based resins, terpene-based resins and petroleum resins, based on 100 parts by weight of the sum of amounts of the syndiotactic propylene polymer (AA) and the propylene.α-olefin copolymer (B3). 
     
     
         22 . The propylene-based polymer composition (X3) according to  claim 19 , further comprising 0.1 to 500 parts by weight of a non-crosslinked or partially crosslinked olefin-based thermoplastic elastomer (C2) based on 100 parts by weight of the sum of amounts of the syndiotactic propylene polymer (AA) and the propylene.α-olefin copolymer (B3). 
     
     
         23 . A molded product formed using the propylene-based polymer composition according to  claim 1 . 
     
     
         24 . A sheet obtained from the propylene-based polymer composition (X1) according to  claim 1 . 
     
     
         25 . An unstretched or stretched film obtained from the propylene-based polymer composition (X1) according to  claim 1 . 
     
     
         26 . A laminate comprising the film according to  claim 25 . 
     
     
         27 . A non-woven fabric obtained from the propylene-based polymer composition (X1) according to  claim 1 . 
     
     
         28 . A molded product formed using the pellets according to  claim 10 . 
     
     
         29 . A sheet obtained from the pellets according to  claim 10 . 
     
     
         30 . An unstretched or stretched film obtained from the pellets according to  claim 10 . 
     
     
         31 . A laminate comprising the film according to  claim 30 . 
     
     
         32 . A non-woven fabric obtained from pellets according to  claim 10 . 
     
     
         33 . A molded product formed using the propylene-based polymer composition (X2) according to  claim 11 . 
     
     
         34 . A sheet obtained from the propylene-based polymer composition (X2) according to  claim 11 . 
     
     
         35 . An unstretched or stretched film obtained from the propylene-based polymer composition (X2) according to  claim 11 . 
     
     
         36 . A laminate comprising the film according to  claim 35 . 
     
     
         37 . A non-woven fabric obtained from the propylene-based polymer composition (X2) according to  claim 11 . 
     
     
         38 . A molded product formed using the propylene-based polymer composition (X3) according to  claim 19 . 
     
     
         39 . A sheet obtained from the propylene-based polymer composition (X3) according to  claim 19 . 
     
     
         40 . An unstretched or stretched film obtained from the propylene-based polymer composition (X3) according to  claim 19 . 
     
     
         41 . A laminate comprising the film according to  claim 40 . 
     
     
         42 . A non-woven fabric obtained from the propylene-based polymer composition (X3) according to  claim 19 .