Catalyst for synthesizing polyolefins
View Patent ↗The present invention relates to a method for producing a high-molecular-weight copolymer of polar group-containing allyl monomers comprising monomer units represented by formulae (3) and (4) (in the formulae, R 1 represents a hydrogen atom (H) or hydrocarbon group having 1 to 6 carbon atoms; R 2 represents —OH, —OCOR 3 (R 3 represents hydrocarbon group having 1 to 5 carbon atoms), —N(R 4 ) 2 (R 4 represents a hydrogen atom or hydrocarbon group having 1 to 5 carbon atoms); and n and m are a value representing the molar ratio of each of the monomer units), which has few branches and unsaturated group at the molecular end, by copolymerizing olefin and an allyl compound using a metal complex of group 10 elements in the periodic system represented by formula (I) as a catalyst. The present invention enables providing a high-molecular-weight copolymer of polar group-containing allyl monomers, which copolymer has a novel structure, is available for various applications and has been considered to be difficult to synthesize by other polymerization methods such as radical polymerization; and a method for producing the same.
1. A method for producing copolymers, comprising a process of reacting non-polar olefins with polar olefins under polymerization conditions in the presence of a catalyst composition containing an organometallic compound,
wherein polar olefins are represented by formula (VII)
CH 2 ═CR 13 R 14 (VII)
wherein R 13 represents a hydrogen atom or a methyl group; R 14 represents —COOR 15 , —CN, —OCOR 15 , —OR 15 , —CH 2 —OCOR 15 , —CH 2 OH, —CH 2 —N(R 16 ) 2 or —CH 2 —Hal, wherein R 15 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 18 carbon atoms; R 16 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 18 carbon atoms or an alkoxycarbonyl group; and Hal represents a halogen atom, and
wherein the organometallic compound contains bisphosphine monoxide (BPMO) represented by formula (I) and a metal center M comprising elements belonging to Group 10 in the periodic system that forms a complex with BPMO
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure; and A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms.
2. The method for producing copolymers as claimed in claim 1 , wherein both of R 1a and R 1b are isopropyl group or t-butyl group.
3. The method for producing copolymers as claimed in claim 1 , wherein both of R 2a and R 2b are t-butyl group.
4. The method for producing copolymers as claimed in claim claim 1 , wherein R 14 is CH 2 —OCOR 15 , CH 2 OH, —CH 2 —N(R 16 ) 2 or —CH 2 —Hal.
5. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (II)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms;
R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a bivalent group represented by A 2 (A 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic group or a C2-C4 alkylene group;
R 4 represents a neutral electron-donating ligand; R 3 and R 4 may be crosslinked; when R 3 and R 4 are crosslinked, L represents a single bond or a bivalent group selected from an alkylene group, a haloalkylene group, an alkenylene group or an alkynylene group; and when R 3 and R 4 are not crosslinked (that is, when L does not exist), R 4 needs not to exist; and
X − represents a counterion of the cationic organometallic compound.
6. The method for producing copolymers as claimed in claim 5 , wherein ligand R 4 is:
(i) selected from pyridine, a substituted pyridine, a nitrile compound, ammonia, an alkylamine, a substituted alkylamine, an arylamine or a substituted arylamine; or
(ii) represented by formula (1)
(wherein W represents C or S; Z is selected from O, S, NH or NR a (R a represents an alkyl group or an aryl group) and Y needs not to exist; when Y exists, Y is selected from O, S, NH or NR b (R b represents an alkyl group or an aryl group); R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR c (R c represents an alkyl group or an aryl group) or —NR d 2 (R d represents an alkyl group or an aryl group).
7. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (IIa)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms; and
X − represents a counterion of the cationic organometallic compound.
8. The method for producing copolymers as claimed in claim 7 , wherein A 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or substituted or an unsubstituted methylene group.
9. The method for producing copolymers as claimed in claim 7 , wherein R 1a , R 1b , R 2a and R 2b independently represent a branched alkyl group having 3 to 6 carbon atoms.
10. The method for producing copolymers as claimed in claim 7 , wherein X— is selected from SbF 6 − , BPh 4 − , BArF 4 − (ArF 4 is [3,5-(CF 3 ) 2 C 6 H 3 ] 4 ), BF 4 − or PF 6 − .
11. The method for producing copolymers as claimed in claim 7 , wherein M is palladium.
12. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (III)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms;
X − represents a counterion of the cationic organometallic compound;
R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group; R 7 , R 8 and R 9 independently represent an alkyl group or an alkoxy group having 1 to 4 carbon atoms.
13. The method for producing copolymers as claimed in claim 12 , wherein A 1 is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or a substituted or unsubstituted methylene group.
14. The method for producing copolymers as claimed in claim 12 , wherein R 1a , R 1b , R 2a and R 2b independently represent a branched alkyl group having 3 to 6 carbon atoms.
15. The method for producing copolymers as claimed in claim 12 , wherein X − is selected from SbF 6 − , BPh 4 − , BArF 4 − (ArF 4 is [3,5-(CF 3 ) 2 C 6 H 3 ] 4 ), BF 4 − and or PF 6 − .
16. The method for producing copolymers as claimed in claim 12 , wherein M is palladium.
17. The method for producing copolymers as claimed in claim 1 , wherein the organometallic compound is represented by formula (IV)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
A 1 represents an arylene group, a monocyclic heteroarylene group, a bivalent heterocyclic group, an alkylene group having 1 to 2 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, or a cycloalkenylene group having 3 to 10 carbon atoms;
A 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic group or a C2-C4 alkylene group;
X − represents a counterion of the cationic organometallic compound;
W represents C or S;
Z is selected from O, S, NH or NR a (R a represents an alkyl group or an aryl group) and Y needs not to exist; when Y exists, Y is selected from O, S, NH or NR b (R b represents an alkyl group or an aryl group); and
R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR c (R c represents an alkyl group or an aryl group) or —NR d 2 (R d represents an alkyl group or an aryl group).
18. The method for producing copolymers as claimed in claim 17 , wherein the organometallic compound is represented by formula (V)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
A 2 represents an arylene group, a monocyclic heteroarylene group, a monocyclic cycloalkylene group, a monocyclic cycloalkenylene group, a monocyclic heterocycloalkylene group, a monocyclic heterocycloalkenylene group, a heterocyclic group or a C2-C4 alkylene group;
R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR c , wherein R c represents an alkyl group or an aryl group) or —NR d 2 and wherein R d represents an alkyl group or an aryl group;
X − represents a counterion of the cationic organometallic compound; and
R 11 may not exist or represents an alkyl group having 1 to 10 carbon atoms, 1 to 4 of which exist on a benzene ring, and the existing two or more R 11 's may be the same or different with each other.
19. The method for producing copolymers as claimed in claim 18 , wherein the organometallic compound is represented by formula (VI)
wherein
M represents an element belonging to Group 10 in the periodic system;
R 1a , R 1b , R 2a and R 2b may be the same or different with each other, and independently represent a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 14 carbon atoms, a substituted or unsubstituted biphenyl group or a substituted or unsubstituted aryl group; a pair of R 1a and R 1b and a pair of R 2a and R 2b may be bonded to form a ring structure;
R 5 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, —OR c , wherein R c represents an alkyl group or an aryl group) or —NR d 2 and wherein R d represents an alkyl group or an aryl group;
R 11 may not exist or represents an alkyl group having 1 to 10 carbon atoms, 1 to 4 of which exist on a benzene ring, and the existing two or more R 11 's may be the same or different with each other; R 12 does not exist, or represents an alkyl group having 1 to 10 carbon atoms, which is substituted with an arbitrary replaceable hydrogen in a benzene ring, and when two or more R 12 exist, they be the same or different from each other; and
X − represents a counterion of the cationic organometallic compound.
20. The method for producing copolymers as claimed in claim 17 , wherein R 1a , R 1b , R 2a and R 2b are independently a branched alkyl group having 3 to 14 carbon atoms.
21. The compound method for producing copolymers as claimed in claim 17 , wherein X − is selected from SbF 6 − , BPh 4 − , BArF 4 − where ArF 4 is [3,5-(CF 3 ) 2 C 6 H 3 ] 4 , BF 4 − or PF 6 − .