Catalyst for olefin/styrene copolymerization, and process for producing olefin/styrene copolymer
View Patent ↗Catalysts for copolymerization of olefins and styrenes, comprising (A) a transition metal compound, (B) an oxygen-containing compound and/or a compound capable of reacting with a transition metal compound to form an ionic complex, (C) a specific compound such as a reaction product of triphenylmethyl alcohol and triisobutylaluminium, and optionally (D) an alkylating agent, and methods for producing olefin-styrene copolymers in the presence of such catalysts, which catalysts have the advantages of enhancing the copolymerization activity and reducing the amount of the promoter such as oxygen-containing compounds, etc, and using them, olefin-styrene copolymers can be produced efficiently and inexpensively.
1. A catalyst for copolymerization of olefins and styrenes, which comprises:
(A) a transition metal compound represented by any of the following general formulae (2) to (6):
Q 1 a (C 5 H 5-a-b R 8 b )(C 5 H 5-a-c R 9 c )M 1 X 1 Y 1 (2)
Q 2 a (C 5 H 5-a-d R 10 d ) Z 1 M 1 X 1 Y 1 (3)
(C 5 H 5 ,R 11 e ) M 1 X 1 Y 1 W 1 (4)
M 1 X 1 Y 1 W 1 U 1 (5)
L 1 L 2 M 2 X 1 Y 1 (6)
in which Q 1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C 5 H 5-a-b R 8 b ) and (C 5 H 5-a-c R 9 c );Q 2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C 5 H 5-a-d ,R 10 d ) and the group Z 1 ; R 8 , R 9 , R 10 and R 11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may bc the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a−2; e is an integer of from 0 to 5; M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M 2 represents a transition metal of Groups 8 to 10 of the Periodic Table; L 1 and L 2 each represent a coordination-bonding ligand; X 1 , Y 1 , Z 1 , W 1 and U 1 each represent a covalent-bonding or ionic-bonding ligand; and L 1 , L 2 , X 1 , Y 1 , Z 1 , W 1 and U 1 may be bonded to each other to form a cyclic structure,
(B) an oxygen-containing compound represented by any of the following general formulae (8) to (9):
wherein R 21 to R 27 each represent an alkyl group having from 1 to 8 carbon atoms and may be the same or different, and R 26 and R 2 ′ may be the same or different. Y 2 to Y 6 each represent an element of Group 13 of the Periodic Table, Y 2 to Y 4 may be the same or different; and Y 5 and Y 6 may be the same or different, a to d each indicates a number of from 0 to 50, but (a+b) and (c+d) each must be at least 1,
(C) a compound of a general formula (1):
((R 1 ) 3 —X—Y)n-Z—(R 2 )m-n (1)
wherein R 1 a phenyl group; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R 2 represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m-1),
and optionally,
(D) an alkylating agent represented by any of the following general formulae (12) to (14):
R 31 m Al(OR 32 ) n X 3−m−n (12)
R 31 2 Mg (13)
R 31 2 Zn (14)
wherein R 31 and R 32 each represent an alkyl group having from 1 to 8 carbon atoms; X represents a hydrogen atom or a halogen atom, 0<m≦3, 0≦n<3.
2. A catalyst for copolymerization of olefins and styrenes, which comprises:
(A) a transition metal compound,
(C) a compound of a general formula (1):
((R 1 ) 3 —X—Y)n-Z—(R 2 )m-n (1)
wherein R 1 represents a phenyl group; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R 2 represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m-1),
and optionally,
(D) an alkylating agent.
3. The catalyst as claimed in claim 1 for copolymerization of olefins and styrenes, wherein, in (C), X is carbon, Y is oxygen and Z is aluminium.
4. The catalyst as claimed in claim 1 for copolymerization of olefins and styrenes, wherein the compound (C) is a reaction product of <1>at least one selected from compounds of a general formula, (R 1 ) 3 —C—OR 3 , R 4 —CO—R 5 or R 6 —CO—OR 7 , with <2>a compound of a general formula, Z (R 2 )m, wherein R 1 represents a phenyl group, R 3 , R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and [[R 1 ,]] R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and [[R 1 ,]] R 3 , R 4 , R 5 , R 6 and R 7 may be optionally bonded to each other to form a cyclic structure; Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R 2 represents a hydrocarbon group.
5. A catalyst for copolymerization of olefins and styrenes, which comprises:
(A) a transition metal compound,
(B) an oxygen-containing compound, and/or a compound capable of reacting with a transition metal compound to form an ionic complex,
(C1) at least one selected from compounds of a general formula, (R 1 ) 3 —C—OR 3 , R 4 —CO—R 5 or R 6 −CO—OR 7 (In these formulae, R 1 represents a phenyl group R 3 , R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and [R 1 ] R 3 , R 4 , R 5 , R 6 and R 7 may be the same different, and [R 1 ] R 3 , R 4 , R 5 , R 6 and R 7 may be optionally bonded to each other to form a cyclic structure,)
(C2) a compound of a general formula, Z(R 2 )m. (In this formula; Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R 2 represents a hydrocarbon group, and optionally,
(D) an alkylating agent.
6. A catalyst for copolymerization of olefins and styrenes, which comprises:
(A) a transition metal compound,
(C1) at least one selected from compounds of a general formula, (R 1 ) 3 —C—OR 3 , R 4 —CO—R 5 or R 6 —CO—OR 7 (In these formulae, R 1 represents a phenyl group, R 3 , R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an thioaryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and [R 1 ] R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and [R 1 ] R 3 ‘R’, R 4 , R, R 6 and R 7 maybe optionally bonded to each other to form a cyclic structure,
(C2) a compound of a general formula, Z(R 2 ) m , wherein Z represents a metal element of Groups 2 to 13; m is a integer, indicating the valency of the metal element Z; and R 2 represents a hydrocarbon group,
and optionally,
(D) an alkylating agent.
7. The catalyst as claimed in claim 1 for copolymerization of olefins and styrenes, wherein R 2 is an alkyl group having at least 2 carbon atoms.
8. The catalyst as claimed in claim 4 for copolymerization of olefins and styrenes, wherein Z is aluminium.
9. The catalyst as clamed in claim 1 for copolymerization of olefins and styrenes, wherein, in the transition metal compound (A) of formula (4), the group (C 5 H 5-e R 11 e ) is represented by any of the following general formulae (I) to (VII):
wherein A represents an element of Group 13, 14, 15 or 16, and plural A's may be the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
10. A method for producing olefin-styrene copolymers, which comprises polymerizing olefins and styrenes in the presence of the copolymerization catalyst of claim 1 .
11. The catalyst as claimed in claim 2 for copolymerization of olefins and styrenes, wherein, in (C), X is carbon, Y is oxygen and Z is aluminium.
12. The catalyst as claimed in claim 2 for copolymerization of olefins and styrenes, wherein the compound (C) is a reaction product of <1>at least one selected from compounds of a general formula, (R 1 ) 3 —C—OR 3 , R 4 —CO—R or R 6 —CO—OR 7 , with <2>a compound of a general formula, Z (R 2 ) m . (In these formulae, R 1 represents a phenyl group, R 3 , R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, an [R 1 ] R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different, and [R 1 ] R 3 , R 4 , R 5 , R 6 and R 7 may be optionally bonded to each other to form a cyclic structure; Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R 2 represents a hydrocarbon group).
13. The catalyst as claimed in claim 2 for copolymerization of olefins and styrenes, wherein R 2 is an alkyl group having at least 2 carbon atoms.
14. The catalyst as claimed in claim 5 for copolymerization of olefins and styrenes, wherein R 2 is an alkyl group having at least 2 carbon atoms.
15. The catalyst as claimed in claim 6 for copolymerization of olefins and styrenes, wherein R 2 is an alkyl group having at least 2 carbon atoms.
16. The catalyst as claimed in claim 5 for copolymerization of olefins and styrenes, wherein Z is aluminium.
17. The catalyst as claimed in claim 6 for copolymerization of olefins and styrenes, wherein Z is aluminium.
18. The catalyst as claimed in claim 2 for copolymerization of olefins and styrenes, wherein the transition metal compound (A) is represented by any of the following general formulae (2) to (6):
Q 1 a (C5H 5-a-b R 8 b ) (C 5 H 5-a-d R 9 c )M 1 X 1 Y 1 (2)
Q 2 a (C 5 H 5-a-d R 10 d ) Z 1 M 1 X 1 Y 1 (3)
(C 5 H 5-e R 11 e ) M 1 X 1 Y 1 W 1 (4)
M 1 X 1 Y 1 W 1 U 1 (5)
L 1 L 2 M 2 X 1 Y 1 (6)
in which Q 1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C 5 H 5-a-b R 8 b ) and (C 5 H 5-a-c R 9 c ); Q 2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C 5 H 5-a-d R 10 d ) and the group Z 1 ; R 8 , R 9 , R 10 and R 11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; c is an integer of from 0 to 5; M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M 2 represents a transition metal of Groups 8 to 10 of the Periodic Table; L 1 and L 2 each represent a coordination-bonding ligand; X 1 , Y 1 , Z 1 , W 1 and U 1 each represent a covalent-bonding or ionic-bonding ligand; and L 2 , L 2 , X 1 , Y 1 , Z 1 , W 1 and U 1 may be bonded to each other to form a cyclic structure.
19. The catalyst as claimed in claim 5 for copolymerization of olefins and styrenes, wherein the transition metal compound (A) is represented by any of the following general formulae (2) to (6):
Q 1 a (C 5 H 5-a-b R 8 b ) (C 5 H 5-a-c R 9 c )M 1 X 1 Y 1 (2)
Q 2 a (C 5 H 5-a-d R 10 d ) Z 1 M 1 X 1 Y 1 (3)
(C 5 H 5-e R 11 e ) M 1 X 1 Y 1 W 1 (4)
M 1 X 1 Y 1 W 1 U 1 (5)
L 1 L 2 M 2 X 1 Y 1 (6)
in which Q 1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C 5 H 5-a-b R 8 b ) and (C 5 H 5-a-c R 9 c ); Q 2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C 5 H 5-a-d R 10 d ) and the group Z 1 ; R 8 , R 9 , R 10 and R 11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; e is an integer of from 0 to 5; M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M 2 represents a transition metal of Groups 8 to 10 of the Periodic Table; L 1 and L 2 each represent a coordination-bonding ligand; X 1 , Y 1 , Z 1 , W 1 and U 1 each represent a covalent-bonding or ionic-bonding ligand; and L 1 , L 2 , X 1 , Y 1 , Z 1 , W 1 and U 1 may be bonded to each other to form a cyclic structure.
20. The catalyst as claimed in claim 6 for copolymerization of olefins and styrenes, wherein the transition metal compound (A) is represented by any of the following general formulae (2) to (6):
Q 1 a (C 5 H 5-a-b R 8 b )(C 5 H 5-a-c R 9 c )M 1 X 1 Y 1 (2)
Q 2 a (C 5 H 5-a-d R 10 d ) Z 1 M 1 X 1 Y 1 (3)
(C 5 H 5-a-e R 11 e ) M 1 X 1 Y 1 W 1 (4)
M 1 X 1 Y 1 W 1 U 1 (5)
L 1 L 2 M 2 X 1 Y 1 (6)
in which Q 1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H 5-a-b R 8 b ) and (C5H 5-a-c R 9 c ); Q 2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C 5 H 5a-d R 10 d ) and the group Z 1 ; R 8 , R 9 , R 10 and R 11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; e is an integer of from 0 to S; M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M 2 represents a transition metal of Groups 8 to 10 of the Periodic Table; L 1 and L 2 each represent a coordination-bonding ligand; X 1 , Y 1 , Z 1 , W 1 and U 1 each represent a covalent-bonding or ionic-bonding ligand; and L 1 , L 2 , X 1 , Y 1 , Z 1 , W 1 and U 1 may be bonded to each other to form a cyclic structure.
21. The catalyst as claimed in claim 2 for copolymerization of olefins and styrenes, wherein, in the transition metal compound (A) of formula (4), the group (C 5 H 5 R 11 ) is represented by any of the following general formulae (1) to (VII):
wherein A represents an element of Group 13, 14, 15 or 16, and plural A's may be the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
22. The catalyst as claimed in claim 5 for copolymerization of olefins and styrenes, wherein, in the transition metal compound (A) of formula (4), the group (C 5-e H 5 ,R 11 e ) is represented by any of the following general formulae (1) to (VII):
wherein A represents an element of Group 13, 14, 15 or 16, and plural A's may be the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
23. The catalyst as claimed in claim 6 for copolymerization of olefins and styrenes, wherein, in the transition metal compound (A) of formula (4), the group (C 5 H 5-e R 11 e ) is represented by any of the following general formulae (I) to (VII):
wherein A represents an element of Group 13, 14, 15 or 16, and plural A's may be the same or different; K represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
24. A method for producing olefin-styrene copolymers, which comprises polymerizing olefins and styrenes in the presence of the copolymerization catalyst of claim 2 .
25. A method for producing olefin-styrene copolymers, which comprises polymerizing olefins and styrenes in the presence of the copolymerization catalyst of claim 5 .
26. A method for producing olefin-styrene copolymers, which comprises polymerizing olefins and styrenes in the presence of the copolymerization catalyst of claim 6 .