Propylene polymer and composition containing the same, molded object and laminate comprising these, and processes for producing propylene polymer and composition containing the same

Abstract

A propylenic polymer according to the present invention or a composition thereof have an excellent melt flowability and contains a less amount of stickiness-causing components, and also has a low modulus and is pliable, and is capable of providing a transparent molded article, thus being useful as a substitute for a pliable vinyl chloride resin. In addition, a molded article made therefrom exhibits an excellent heat seal performance at a low temperature, and is excellent in terms of transparency and rigidity. Specifically, it has an isotactic pentad fraction (mmmm), which indicates a stereoregularity, of 30 to 80%, a molecular weight distribution (Mw/Mn) of 3.5 or less and an intrinsic viscosity [η] of 0.8 to 5 dl/g.

1 - 15 . (canceled) 
   
   
       16 . A method for producing a propylene homopolymer, comprising:
 homopolymerizing propylene in the presence of a polymerization catalyst, to obtain said propylene homopolymer,   said polymerization catalyst comprising:   (A) a transition metal compound represented by Formula (I) shown below and   (B) is at least one component selected from the group consisting of (B-1) or (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same as or different from each other, X denotes a σ-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent crosslinking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)−2, and r is an integer of 0 to 3;
 wherein said propylene homopolymer satisfies the following requirements (1) and (2): 
 (1) the amount of the components which are dissolved out into hexane at 25° C. (H25) ranges from 0 to 80% by weight; and, 
 (2) no melting point (Tm(° C.)) is observed in DSC or, when any Tm is observed then the Tm and the fusion endothermic calorie ΔH(J/g) are in the relationship represented by the following formula:
   ΔH≧6×(Tm−140). 
 
 
   
   
       17 . A method for producing a propylenic copolymer wherein propylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms is copolymerized in the presence of a polymerization catalyst comprising:
 (A) a transition metal compound represented by Formula (I) shown below and (B) is at least one component selected from the group consisting of (B-1) and (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same as or different from each other, X denotes a σ-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent linking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)−2, and r is an integer of 0 to 3;
 wherein said propylenic copolymer satisfies the following requirements (1) and (2):
 (1) the stereoregularity index (P) determined by a  13 C-NMR ranges from 55 to 90% by mole; and, 
 (2) the amount of the components which are dissolved out at 25° C. or lower (W25) in a temperature-raising chromatography ranges from 20 to 100% by weight. 
 
 
   
   
       18 - 64 . (canceled) 
   
   
       65 . A method for producing a propylene homopolymer, comprising:
 homopolymerizing propylene in the presence of a polymerization catalyst, to obtain said propylene homopolymer,   said polymerization catalyst comprising:   (A) a transition metal compound represented by Formula (I) shown below and   (B) is at least one component selected from the group consisting of (B-1) or (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same to as or different from each other, X denotes a σ-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent crosslinking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)−2, and r is an integer of 0 to 3;
 wherein said propylene homopolymer satisfies the following requirements (1) to (3): 
 (1) the amount of the components which are dissolved out at 25° C. or lower (W25) in a temperature-raising chromatography ranges from 20 to 100% by weight; 
 (2) the amount of the components which are dissolved out into hexane at 25° C. (H25) ranges from 0 to 80% by weight; and, 
 (3) no melting point (Tm(° C.)) is observed in DSC or, when any Tm is observed then the Tm and the fusion endothermic calorie ΔH(J/g) are in the relationship represented by the following formula:
   ΔH≧6×( Tm− 140). 
 
 
   
   
       66 . A method for producing a propylene homopolymer, comprising:
 homopolymerizing propylene in the presence of a polymerization catalyst, to obtain said propylene homopolymer,   said polymerization catalyst comprising:   (A) a transition metal compound represented by Formula (I) shown below and   (B) is at least one component selected from the group consisting of (B-1) or (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same to as or different from each other, X denotes a 6-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent crosslinking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)−2, and r is an integer of 0 to 3;
 wherein said propylene homopolymer satisfies the following requirements (1) to (3): 
 (1) the meso-pentad fraction (mmmm (in percentage terms by mole)) ranges from 20 to 60% by mole; 
 (2) the racemi-pentad fraction (rrrr) and (1−mmmm) are in the relationship represented by the following formula:
   [ rrrr /(1 −mmmm )]≦0.1 
 
 
     wherein the racemi-pentad fraction (rrrr) and the meso-pentad fraction (mmmm) are not in percentage terms; and,
 (3) the amount of the components which are dissolved out at 25° C. or lower (W25) in a temperature-raising chromatography ranges from 20 to 100% by weight. 
 
   
   
       67 . A method for producing a propylene homopolymer, comprising:
 homopolymerizing propylene in the presence of a polymerization catalyst, to obtain said propylene homopolymer,   said polymerization catalyst comprising:   (A) a transition metal compound represented by Formula (I) shown below and   (B) is at least one component selected from the group consisting of (B-1) or (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same to as or different from each other, X denotes a σ-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent crosslinking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)−2, and r is an integer of 0 to 3;
 wherein said propylene homopolymer has a molecular weight distribution (Mw/Mn) determined by a gel permeation chromatography (GPC) of 4 or less and/or an intrinsic viscosity [η] determined in a tetralin solvent at 135° C. of 0.5 to 15.0 dl/g. 
 
   
   
       68 . A method for producing a propylenic copolymer, comprising: copolymerizing propylene and ethylene and/or an α-olefin having 4 to 20 carbon atoms in the presence of a polymerization catalyst,
 said polymerization catalyst comprising:   (A) a transition metal compound represented by Formula (I) shown below and   (B) is at least one component selected from the group consisting of (B-1) and (B-2), wherein (B-1) is a compound which forms an ionic complex by reacting with a transition metal compound as a component (A) or a derivative of the component (A), and (B-2) is an aluminoxane:   
     
       
         
         
             
             
         
       
     
     in which M denotes a metal element of Group 3 to Group 10 or of lanthanoids in the periodic table, each of E 1  and E 2  denotes a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group is linked with each other via A 1  and A 2  and may be the same as or different from each other, X denotes a σ-binding ligand, and, when two or more Xs are present they may be the same or different, and each may be linked with another X, E 1 , E 2  or Y; Y denotes a Lewis base, and, when two or more Ys are present they may be the same or different, and each may be linked with another Y, E 1 , E 2  or X, each of A 1  and A 2  denotes a divalent linking group combining two ligands including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR—, —PR—, —P(O)R—, —BR— or —AlR— wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and each may be the same as or different from each other; q is an integer of 1 to 5 and represents (valency of M)-2, and r is an integer of 0 to 3;
 wherein said propylenic copolymer has a molecular weight distribution (Mw/Mn) determined by a gel permeation chromatography (GPC) of 4 or less and/or an intrinsic viscosity [1] determined in a tetralin solvent at 135° C. of 0.5 to 15.0 dl/g.