Production method for cyclic olefin copolymer and catalyst composition for copolymerization of norbornene monomer and ethylene

Patent metadata

Field	Value
Publication number	US-11795256-B2
Application number	US-202118003424-A
Country	US
Kind code	B2
Filing date	Jun 23, 2021
Priority date	Jun 29, 2020
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

A production method for a cyclic olefin copolymer which is capable of efficiently producing a cyclic olefin copolymer by copolymerizing monomers including a norbornene monomer and ethylene while suppressing the formation of a polyethylene-like impurity, and a catalyst composition for the copolymerization of a norbornene monomer and ethylene. Monomers including a norbornene monomer and ethylene are polymerized in the presence of a metal-containing catalyst, and the metal-containing catalyst has a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of the periodic table and an atom of Group 15 of the periodic table.

First claim

The invention claimed is:

1. A method for producing a cyclic olefin copolymer comprising a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, the method comprising:
charging at least the norbornene monomer and the ethylene as monomers into a polymerization vessel, and
polymerizing the monomers in the polymerization vessel in presence of a metal-containing catalyst, the metal-containing catalyst having a structure in which a nitrogen atom is bonded to a transition metal of Group 4 of periodic table and an atom of Group 15 of periodic table,
wherein the metal-containing catalyst is a metal-containing compound represented by formula (a1):

wherein in the formula (a1), M represents Ti, Zr or Hf, X represents an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or a halogen atom, L 1 represents a group represented by formula (ala) or (a1b):

wherein in the formula (a1a), R a1 to R a5 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms and optionally containing a heteroatom, or an inorganic substituent, two groups adjacent on the 5-membered ring of R a1 to R a5 are optionally bonded to each other to form a ring, wherein in the formula (a1b), R a6 to R a8 are identical to or different from one another, and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms
and optionally containing a heteroatom, or an inorganic substituent, two groups selected from R a6 to R a8 are optionally bonded to each other to form a ring,
wherein the organic substituent as R a6 to R a8 in the formula (a1b) is a group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, an α-naphthylcarbonyl group, a β-naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a monosubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and a disubstituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and

L 2 represents the group represented by the formula (a1b)), and
wherein the norbornene monomer is one or more selected from a norbornene and a substituted norbornene represented by formula (I):

wherein in the formula (I), R 1 to R 8 are identical to or different from one another, and are selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms,
R 9 to R 12 are identical to or different from one another, and are selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an unsubstituted aromatic hydrocarbon group, and an aralkyl group,
R 9 and R 10 or R 11 and R 12 are not taken together to form a divalent hydrocarbon group,
R 9 or R 10 and R 11 or R 12 optionally form a ring with each other,
the ring that R 9 or R 10 and R 11 or R 12 form is not a ring having a double bond,
n represents 0 or a positive integer,
when n is two or more, R 5 to R 8 are identical to or different from each other in the respective repeating units, and
when n is 0, at least one of R 1 to R 4 and R 9 to R 12 is not a hydrogen atom.

2. The method for producing a cyclic olefin copolymer according to claim 1 , wherein the atom of Group 15 of the periodic table is a phosphorus atom.

3. The method for producing a cyclic olefin copolymer according to claim 1 , wherein the transition metal of Group 4 of the periodic table is Ti.

4. The method for producing a cyclic olefin copolymer according to claim 1 , wherein the polymerizing of the monomers is performed in the presence of the metal-containing catalyst and a co-catalyst.

5. The method for producing a cyclic olefin copolymer according to claim 4 , wherein the co-catalyst comprises at least one of an aluminoxane and a borate compound.

6. The method for producing a cyclic olefin copolymer according to claim 1 , wherein the polymerizing of the monomers is performed in the presence of a hydrocarbon solvent.

7. The method for producing a cyclic olefin copolymer according to claim 1 , wherein a DSC curve obtained in measurement of a sample of the cyclic olefin copolymer according to a method defined in JIS K7 121 using a differential scanning calorimeter in a nitrogen atmosphere under a condition of a rate of temperature increase of 20° C./min shows no peak of a melting point assigned to a polyethylene-like impurity in a range of 100° C. to 140° C.

Assignees

• Polyplastics Co

Inventors

• Wakitani Naoyuki
• Tada Tomoyuki

Classifications

• C08F232/04 Primary

  having one carbon-to-carbon double bond · CPC title

• C08F2/06

  Organic solvent · CPC title

• C08F4/083

  an alkali metal bound to oxygen · CPC title

• C08F4/30

  Inorganic compounds · CPC title

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title