Method for producing polar group-containing olefin copolymers
View Patent ↗The present invention relates to a method of producing a polymer in the method for producing a copolymer of olefin and a polar group-containing monomer represented by formula (1): C(R 1 ) 2 ═C(R 1 )(C(R 1 ) 2 ) n R 2 (1) (in the formula, the symbols have the same meanings as described in the description), the method comprising using a complex of a metal in Group 10 of the periodic table as a catalyst; and supplying a catalyst solution separated from a polymer after the polymerization reaction to a polymerization reaction system to recycle and re-use the catalyst. The production method of the present invention can dramatically reduce the catalyst cost.
1. A method of producing a polymer in the method for producing a copolymer of olefin and a polar group-containing monomer represented by formula (1):
C(R 1 ) 2 ═C(R 1 )(C(R 1 ) 2 ) n R 2 (1)
(in the formula, three to five R 1 's may be identical to each other or different from each other, each representing a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; R 2 represents —OR 2-1 , —SR 2-1 , —OCOR 2-1 where R 2-1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, —N(R 2-2 ) 2 where two R 2-2 's may be identical to each other or different from each other, each representing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, —COR 2-3 , or —COOR 2-3 where R 2-3 represents a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom; and n represents 0 or 1), the method comprising using a complex of a metal in Group 10 of the periodic table as a catalyst; and supplying a catalyst solution separated from a polymer after the polymerization reaction to a polymerization reaction system to recycle and re-use the catalyst,
wherein the catalyst made of the complex of the metal in Group 10 of the periodic table is represented by formula (C1):
(in the formula, M represents a metal atom in Group 10 of the periodic table; L 1 represents a group having a nitrogen atom (N), a phosphorus atom (P), or an arsenic atom (As) and bonded to M at the atom; L 2 represents a group having an oxygen atom (O) or a sulfur atom (S) and bonded to M at the atom; L 3 represents an electron-donating ligand; and R 3 represents a hydrogen atom, an acyloxy group, or a hydrocarbon group which has 1 to 30 carbon atoms and which may be substituted by one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group and an acyloxy group); and
wherein the polymer is separated out of the catalyst solution by using a solid-liquid separator selected from the group consisting of a centrifugation separator and a filtration separator.
2. The method of producing a polymer according to claim 1 , wherein the supply of the catalyst solution separated from the polymer after the polymerization reaction to the polymerization reaction system to recycle and re-use the catalyst is carried out without any post-treatment.
3. The method of producing a polymer according to claim 1 , in which the catalyst represented by the general formula (C1) is represented by formula (C2):
(in the formula, M represents a metal atom in Group 10 of the periodic table; X represents a phosphorus atom (P) or an arsenic atom (As); R 3 represents a hydrogen atom, an acyloxy group, or a hydrocarbon group which has 1 to 30 carbon atoms and which may be substituted by one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group and an acyloxy group; Y, R 4 , and R 5 each independently represent a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydrocarbon group which has 1 to 30 carbon atoms and which may be substituted by one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group; R 4 and R 5 may be bonded to each other to form a ring structure; Q represents a divalent group represented in the following brackets “[ ]” in Z[—S(═O) 2 —O-]M, Z[—C(═O)—O-]M, Z[—P(═O)(—OH)—O-]M, or Z[—S-]M where Z and M at the beginning and at the end of the formulae are described to show a bonding direction of the group); Z represents a hydrogen atom or a hydrocarbon which has 1 to 40 carbon atoms and which may be substituted by one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group; Y and Z may be bonded to each other to form a ring structure; R 4 and/or R 5 may be bonded to Y to form a ring structure; and L 3 represents an electron-donating ligand).
4. The method of producing a polymer according to claim 3 , wherein the catalyst represented by formula (C2) is represented by formula (C3):
(In the formula, Y 1 represents a divalent hydrocarbon group which has 1 to 70 carbon atoms and which may be substituted by one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group; and Q, M, X, R 3 , R 4 , R 5 , and L 3 have the same meanings as in formula (C2)).
5. The method of producing a polymer according to claim 4 , in which the catalyst represented by (C3) is represented by formula (C4):
(in the formula, four R 6 's each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, or a halogen atom; and M, R 3 , R 4 , R 5 , and L 3 have the same meanings as in formula (C2)).
6. The method of producing a polymer according to claim 1 , wherein part of a polymerization reaction liquid is continuously withdrawn from a polymerization reactor during the polymerization reaction of the monomer using a continuous polymerization reaction apparatus provided with the polymerization reactor and the solid-liquid separator; the catalyst solution and the polymer are separated in the solid-liquid separator; and the separated catalyst solution is returned to the polymerization reactor without being treated.
7. The method of producing a polymer according to claim 2 , wherein part of a polymerization reaction liquid is continuously withdrawn from a polymerization reactor during the polymerization reaction of the monomer using a continuous polymerization reaction apparatus provided with the polymerization reactor and the solid-liquid separator; the catalyst solution and the polymer are separated in the solid-liquid separator; and the separated catalyst solution is returned to the polymerization reactor without being treated.
8. The method of producing a polymer according to claim 3 , wherein part of a polymerization reaction liquid is continuously withdrawn from a polymerization reactor during the polymerization reaction of the monomer using a continuous polymerization reaction apparatus provided with the polymerization reactor and the solid-liquid separator; the catalyst solution and the polymer are separated in the solid-liquid separator; and the separated catalyst solution is returned to the polymerization reactor without being treated.
9. The method of producing a polymer according to claim 4 , wherein part of a polymerization reaction liquid is continuously withdrawn from a polymerization reactor during the polymerization reaction of the monomer using a continuous polymerization reaction apparatus provided with the polymerization reactor and the solid-liquid separator; the catalyst solution and the polymer are separated in the solid-liquid separator; and the separated catalyst solution is returned to the polymerization reactor without being treated.
10. The method of producing a polymer according to claim 5 , wherein part of a polymerization reaction liquid is continuously withdrawn from a polymerization reactor during the polymerization reaction of the monomer using a continuous polymerization reaction apparatus provided with the polymerization reactor and the solid-liquid separator; the catalyst solution and the polymer are separated in the solid-liquid separator; and the separated catalyst solution is returned to the polymerization reactor without being treated.