Ethylene copolymer and aromatic vinyl graft copolymer and method for producing the same

Abstract

The present invention provides resin materials endowed with excellent heat resistance, solvent resistance, tensile elongation, toughness, and transparency. Specifically, there are provided an ethylene copolymer having a vinyl group attributed to a diene monomer in the molecular chain and comprising an aromatic vinyl monomer (A), ethylene (B) and a diene monomer (C), and an aromatic vinyl graft copolymer which is a graft copolymerization product of an aromatic vinyl monomer (H) and an ethylene copolymer macromer (I).

What is claimed is:  
     
         1 . An ethylene copolymer comprising an aromatic vinyl monomer (A), ethylene (B) and a diene monomer (C), and having in the molecular chain a vinyl group attributed to a diene monomer, wherein recurrent units attributed to aromatic vinyl monomer (A) is 1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol % and recurrent units attributed to diene monomer (C) is 0.001-10 mol %.  
     
     
         2 . An ethylene copolymer comprising an aromatic vinyl monomer (A), ethylene (B), a diene monomer (C), and α-olefin (D), and having in the molecular chain a vinyl group attributed to a diene monomer, wherein recurrent units attributed to aromatic vinyl monomer (A) is 1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol %, recurrent units attributed to diene monomer (C) is 0.001-10 mol % and recurrent units attributed to α-olefin (D) is 0-90 mol % (exclusive of 0).  
     
     
         3 . The ethylene copolymer according to  claim 1 , wherein the diene monomer (C) is a diene having a styrenic vinyl group.  
     
     
         4 . The ethylene copolymer according to  claim 2 , wherein the diene monomer (C) is a diene having a styrenic vinyl group.  
     
     
         5 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3 , which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         6 . A method for producing an ethylene copolymer recited in  claim 2 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y3, which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         7 . A method for producing an ethylene copolymer recited in  claim 3 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3 , which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y4 and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         8 . A method for producing an ethylene copolymer recited in  claim 4 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3 , which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         9 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound represented by the following formula (1):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y3, which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1.    
     
     
         10 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound represented by the following formula (2):                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1.    
     
     
         11 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) a compound capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         12 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E), (F) and (G): 
 (E) a transition metal compound;    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3 , which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E): and    (G) an alkylating agent.    
     
     
         13 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E), (F) and (G): 
 (E) a transition metal compound;    (F) an oxygen-containing compound represented by the following formula (1):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3  which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1: and    (G) an alkylating agent.    
     
     
         14 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E), (F) and (G): 
 (E) a transition metal compound;    (F) an oxygen-containing compound represented by the following formula (2):                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and    (G) an alkylating agent.    
     
     
         15 . A method for producing an ethylene copolymer recited in  claim 1 , wherein the respective monomers are copolymerized through use of a catalyst formed of the following components (E), (F) and (G): 
 (E) a transition metal compound;    (F) a compound capable of forming an ionic complex through reaction with transition metal compound (E): and    (G) an alkylating agent.    
     
     
         16 . The method for producing an ethylene copolymer according to  claim 5 , wherein the transition metal compound (E) is represented by the following formula (3):  
       
         
           
           
               
               
           
         
       
       wherein M 1  represents titanium, zirconium, or hafnium; Cp★ represents a cyclopentadienyl group or a substituted cyclopentadienyl group which is bonded to M 1  via a η 5  bonding mode, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, or a substituted octahydrofluorenyl group; X 1  represents a σ ligand; e represents 1 or 2; a plurality of X 1  may be identical to or different from one another and may be linked together via an arbitrary group; Y 6  represents O, S, NR, PR, CR 2 , or a neutral two-electron donor selected from OR, SR, NR 2 , or PR 2 ; Z 1  represents SiR 2 , CR 2 , SiR 2 SiR 2 , CR 2 CR 2 , CR=CR, CRSiR 2 , GeR 2 , BR, or BR 2 ; R represents hydrogen, an alkyl group, an aryl group, a silyl group, a haloalkyl group, a haloaryl group, or a combination of at least two of the above groups selected so as to have 20 or fewer non-hydrogen atoms; and two or more of the above R may further form a condensed ring system with Z 1  or with Y 6  and Z 1 .  
     
     
         17 . An aromatic vinyl graft copolymer which is a graft copolymerization product of an aromatic vinyl monomer (H) and ethylene copolymer macromer (I) which has in the molecular chain a vinyl group attributed to a diene monomer; the ethylene copolymer (I) being obtained through copolymerization of an aromatic vinyl monomer (A), ethylene (B) and a diene monomer (C), wherein recurrent units attributed to aromatic vinyl monomer (A) is 1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol %, and recurrent units attributed to diene monomer (C) is 0.001-10 mol %.  
     
     
         18 . An aromatic vinyl graft copolymer which is a graft copolymerization product of an aromatic vinyl monomer (H) and ethylene copolymer macromer (I) and which has in the molecular chain a vinyl group attributed to a diene monomer; the ethylene copolymer (I) being obtained through copolymerization of an aromatic vinyl monomer (A), ethylene (B), a diene monomer (C) and α-olefin (D), wherein recurrent units attributed to aromatic vinyl monomer (A) is 1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol %, recurrent units attributed to diene monomer (C) is 0.001-10 mol % and recurrent units attributed to α-olefin (D) is 0-90 mol % (exclusive of 0).  
     
     
         19 . An aromatic vinyl graft copolymer according to  claim 17 , wherein the diene monomer (C) is a diene having a styrenic vinyl group.  
     
     
         20 . An aromatic vinyl graft copolymer according to  claim 18 , wherein the diene monomer (C) is a diene having a styrenic vinyl group.  
     
     
         21 . An aromatic vinyl graft copolymer according to  claim 17 , wherein a chain attributed to aromatic vinyl monomer (A) has a stereospecificity of highly syndiotactic structure.  
     
     
         22 . An aromatic vinyl graft copolymer according to  claim 17 , wherein a chain attributed to aromatic vinyl monomer (A) has a stereospecificity of highly syndiotactic structure.  
     
     
         23 . An aromatic vinyl graft copolymer according to  claim 17 , wherein the ethylene copolymer macromer (I) is prepared by use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound;    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3  which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1; and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         24 . An aromatic vinyl graft copolymer according to  claim 17 , wherein the ethylene copolymer macromer (I) is prepared by use of a catalyst formed of the following components (E), (F) and (G): 
 (E) a transition metal compound;    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3  which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1; and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E):    (G) an alkylating agent.    
     
     
         25 . The method for producing an ethylene copolymer according to  claim 23 , wherein the transition metal compound (E) is represented by the following formula (3):  
       
         
           
           
               
               
           
         
       
       wherein M 1  represents titanium, zirconium, or hafnium; Cp★ represents a cyclopentadienyl group or a substituted cyclopentadienyl group which is bonded to M 1  via a η 5  bonding mode, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, or a substituted octahydrofluorenyl group; X 1  represents a σ ligand; e represents 1 or 2; a plurality of X 1  may be identical to or different from one another and may be linked together via an arbitrary group; Y 6  represents O, S, NR, PR, CR 2 , or a neutral two-electron donor selected from OR, SR, NR 2 , or PR 2 ; Z 1  represents SiR 2 , CR 2 , SiR 2 SiR 2 , CR 2 CR 2 , CR=CR, CRSiR 2 , GeR 2 , BR, or BR 2 ; R represents hydrogen, an alkyl group, an aryl group, a silyl group, a haloalkyl group, a haloaryl group, or a combination of at least two of the above groups selected so as to have 20 or fewer non-hydrogen atoms; and two or more of the above R may further form a condensed ring system with Z 1  or with Y 6  and Z 1 .  
     
     
         26 . The method for producing an ethylene copolymer according to  claim 24 , wherein the transition metal compound (E) is represented by the following formula (3):  
       
         
           
           
               
               
           
         
       
       wherein M 1  represents titanium, zirconium, or hafnium; Cp★ represents a cyclopentadienyl group or a substituted cyclopentadienyl group which is bonded to M 1  via a η 5  bonding mode, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, or a substituted octahydrofluorenyl group; X 1  represents a σ ligand; e represents 1 or 2; a plurality of X 1  may be identical to or different from one another and may be linked together via an arbitrary group; Y 6  represents O, S, NR, PR, CR 2 , or a neutral two-electron donor selected from OR, SR, NR 2 , or PR 2 ; Z 1  represents SiR 2 , CR 2 , SiR 2 SiR 2 , CR 2 CR 2 , CR=CR, CRSiR 2 , GeR 2 , BR, or BR 2 ; R represents hydrogen, an alkyl group, an aryl group, a silyl group, a haloalkyl group, a haloaryl group, or a combination of at least two of the above groups selected so as to have 20 or fewer non-hydrogen atoms; and two or more of the above R may further form a condensed ring system with Z 1  or with Y 1  and Z 1 .  
     
     
         27 . The method for producing an aromatic vinyl graft copolymer according to claims  17 , wherein aromatic vinyl monomer (H) is graft-copolymerized with ethylene copolymer macromer (I) through use of a catalyst formed of the following components (E) and (F): 
 (E) a transition metal compound; and    (F) an oxygen-containing compound (i) represented by the following formula (1) or (2):                          wherein, each of R 1  through R 5 , which may be identical to or different from one another, represents a C1-C8 alkyl group; each of Y 1  through Y 3,  which may be identical to or different from one another, represents a Group 13 element; and a and b independently represent numbers between 0 and 50 inclusive, with the proviso that a+b is equal to or greater than 1;                          wherein, each of R 6  and R 7 , which may be identical to or different from each other, represents a C1-C8 alkyl group; Y 4  and Y 5 , which may be identical to or different from each other, represents a Group 13 element; and c and d independently represent numbers between 0 and 50 inclusive, with the proviso that c+d is equal to or greater than 1: and/or a compound (ii) capable of forming an ionic complex through reaction with transition metal compound (E).    
     
     
         28 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the transition metal compound (E) is represented by the following formula (16) or (17):  
       M 10 R 26   u R 27   v R 28   w R 29   4−(u+v+w)    (16) M 11 R 30   x R 31   y R 32   3−(x+y)    (17)  
       wherein each of M 10  and M 11  represents a metal that belongs to Groups 3-6 or the lanthanum group; each of R 26  through R 32  represents an alkyl group, an alkoxy group, an aryl group, an alkylaryl group, an arylalkyl group, an aryloxy group, an acyloxy group, a cyclopentadienyl group, an alkylthio group, an arylthio group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, fluorenyl group, an amino group, an amide group, an acyloxy group, a phosphide group, a halogen atom, or a chelating agent; R 26  through R 29 , or R 30  through R 32  may be identical to or different from each other; each of u, v, and w is an integer between 0 and 4 inclusive; each of x and y is an integer of 0 and 3 inclusive; and two of R 26  through R 29  or R 30  through R 32  may be cross-linked by use of CH 2  or Si(CH 3 ) 2  to form a complex.  
     
     
         29 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the transition metal compound (E) is represented by the following formula (18):  
       T i R 33 X 14 Y 10 Z 2    (18)  
       wherein R 33  represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, or a fluorenyl group, and each of X 14 , Y 10 , and Z 2  represents a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, alkylaryl group, arylalkyl group, C6-C20 aryloxy group, C1-C20 acyloxy group, C1-C50 amino group, amide group, phosphide group, alkyl thio group, arylthio group, or a halogen atom: compounds in which one of X 14 , Y 10 , and Z 2  and R 33  are cross-linked with CH 2 , SiR 2 , etc..  
     
     
         30 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the transition metal compound (E) is represented by the following formula (19):  
       
         
           
           
               
               
           
         
       
       wherein each of R 34  and R 35  represents a halogen atom, C1-c20 alkoxy group, or an acyloxy group; and z is a number between 2 and 20 inclusive.  
     
     
         31 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the transition metal compound (E) is represented by the following formula (20):  
       M 12 R 36 R 37 R 38 R 39    (20)  
       wherein M 12  represents titanium, zirconium, or hafnium; each of R 36  and R 37 , which may be identical to or different from each other, represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group; and each of R 38  and R 39 , which may be identical to or different from each other, represents a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, an amino group, or a C1-C20 thioalkoxy group, wherein R 38  and R 39  may be cross-linked by the mediation of a C1-C5 hydrocarbon group, a C1-C20 alkylsilyl group having 1-5 silicon atoms, or a C1-C20 germanium-containing hydrocarbon group having 1-5 germanium atoms.  
     
     
         32 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the transition metal compound (E) is represented by the following formula (3):  
       
         
           
           
               
               
           
         
       
       wherein M 1  represents titanium, zirconium, or hafnium; Cp★ represents a cyclopentadienyl group or a substituted cyclopentadienyl group which is bonded to M 1  via a η 5  bonding mode, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl group, a substituted hexahydroazulenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group, an octahydrofluorenyl group, or a substituted octahydrofluorenyl group; X 1  represents a σ ligand; e represents 1 or 2; a plurality of X 1  may be identical to or different from one another and may be linked together via an arbitrary group; Y 6  represents O, S, NR, PR, CR 2 , or a neutral two-electron donor selected from OR, SR, NR 2 , or PR 2 ; Z 1  represents SiR 2 , CR 2 , SiR 2 SiR 2 , CR 2 CR 2 , CR=CR, CRSiR 2 , GeR 2 , BR, or BR 2 ; R represents hydrogen, an alkyl group, an aryl group, a silyl group, a haloalkyl group, a haloaryl group, or a combination of at least two of the above groups selected so as to have 20 or fewer non-hydrogen atoms; and two or more of the above R may further form a condensed ring system with Z 1  or with Y 6  and Z 1 .  
     
     
         33 . The method for producing an aromatic vinyl graft copolymer according to  claim 27 , wherein the catalyst further contains an alkylating agent (G).