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US-20260125499-A1 - CATALYST LIQUID AND POLYMERIZABLE COMPOSITION

US20260125499A1US 20260125499 A1US20260125499 A1US 20260125499A1US-20260125499-A1

Abstract

Provided is a catalyst solution comprising a metathesis polymerization catalyst, a coordinating compound containing a phosphorus atom, and a solvent, wherein the metathesis polymerization catalyst is a ruthenium-carbene complex represented by General Formula (1) or (2) below, and the coordinating compound containing a phosphorus atom is contained in an amount such that 6 to 1000 mol of phosphorus atoms are contained relative to 1 mol of ruthenium atoms in the metathesis polymerization catalyst.

Inventors

  • Masaki Takeuchi
  • Atsushi Hara

Assignees

  • RIMTEC CORPORATION

Dates

Publication Date
20260507
Application Date
20231011
Priority Date
20221020

Claims (5)

  1. 1 . A catalyst solution comprising a metathesis polymerization catalyst, a coordinating compound containing a phosphorus atom, and a solvent, wherein the metathesis polymerization catalyst is a ruthenium-carbene complex represented by General Formula (1) or (2) below, and the coordinating compound containing a phosphorus atom is contained in an amount such that 6 to 1000 mol of phosphorus atoms are contained relative to 1 mol of ruthenium atoms in the metathesis polymerization catalyst: where in General Formulae (1) and (2) above, R 1 and R 2 each independently represent a hydrogen atom; a halogen atom; or a C 1 to C 20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; and these groups may be substituted, or may be bonded to each other to form a ring; X 1 and X 2 each independently represent any anionic ligand; L 1 and L 2 each represent a heteroatom-containing carbene compound or phosphines; and at least one of L 1 and L 2 is phosphines.
  2. 2 . The catalyst solution according to claim 1 , wherein L 1 is a compound represented by General Formula (3) or (4) below, and L 2 is phosphines: where in General Formulae (3) and (4) above, R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represent hydrogen atom; halogen atom; or a C 1 to C 20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and these groups may be substituted, or may be bonded to each other to form a ring.
  3. 3 . The catalyst solution according to claim 1 , wherein the phosphines are an optionally substituted trialkylphosphine.
  4. 4 . The catalyst solution according to claim 1 , wherein the coordinating compound containing a phosphorus atom is a compound represented by General Formula (5) below: where in General Formula (5) above, R 9 to R 11 each independently represent an optionally substituted alkyl group or an optionally substituted aryl group.
  5. 5 . A polymerizable composition comprising the catalyst solution according to claim 1 , and a norbornene-based monomer as a polymerizable monomer.

Description

TECHNICAL FIELD The present invention relates to a catalyst solution which has high storage stability and demonstrates high catalytic activity even after long-term storage, and a polymerizable composition obtained using such a catalyst solution. BACKGROUND ART Norbornene-based resins obtained by ring-opening polymerization of a norbornene-based monomer are known for their high mechanical strength, high heat resistance, low hygroscopicity, excellent dielectric properties, and the like, and are used in various applications. For example, as a metathesis polymerization catalyst used for ring-opening polymerization of norbornene-based monomers, Patent Document 1 discloses a ruthenium-carbene complex containing phosphines as ligands. In addition, Patent Document 1 also discloses a polymerizable composition comprising such a ruthenium-carbene complex. However, the ruthenium-carbene complex disclosed in Patent Document 1, which is usually dissolved or dispersed in a solvent and used as a catalyst solution, has a problem of insufficient storage stability during storage as a catalyst solution. RELATED ART DOCUMENT Patent Document Patent Document 1: JP 2001-139668 A SUMMARY OF THE INVENTION Problem to be Solved by the Invention An object of the present invention is to provide a catalyst solution which has high storage stability and demonstrates high catalytic activity even after long-term storage. Means for Solving Problems The present inventor, who has conducted extensive research to achieve the above object, has found that by blending a specific amount of a coordinating compound containing a phosphorus atom with a catalyst solution containing a ruthenium carbene complex containing phosphines as ligands, as a metathesis polymerization catalyst, a catalyst solution which has high storage stability and is capable of demonstrating high catalytic activity even after long-term storage can be provided. This finding has led to completion of the present invention. Specifically, the present invention provides the following embodiments. [1] A catalyst solution comprising a metathesis polymerization catalyst, a coordinating compound containing a phosphorus atom, and a solvent, wherein the metathesis polymerization catalyst is a ruthenium-carbene complex represented by General Formula (1) or (2) below, andthe coordinating compound containing a phosphorus atom is contained in an amount such that 6 to 1000 mol of phosphorus atoms are contained relative to 1 mol of ruthenium atoms in the metathesis polymerization catalyst: where in General Formulae (1) and (2) above, R1 and R2 each independently represent a hydrogen atom; a halogen atom; or a C1 to C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; and these groups may be substituted, or may be bonded to each other to form a ring; X1 and X2 each independently represent any anionic ligand; L1 and L2 each represent a heteroatom-containing carbene compound or phosphines; and at least one of L2 and L2 is phosphines. [2] The catalyst solution according to [1], wherein L1 is a compound represented by General Formula (3) or (4) below, and L2 is phosphines: where in General Formulae (3) and (4) above, R3, R4, R5, R6, R7, and R8 each independently represent a hydrogen atom; a halogen atom; or a C1 to C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; and these groups may be substituted, or may be bonded to each other to form a ring. [3] The catalyst solution according to [1] or [2], wherein the phosphines are an optionally substituted trialkylphosphine. [4] The catalyst solution according to any one of [1] to [3], wherein the coordinating compound containing phosphorus atom is a compound represented by General Formula (5) below: where in General Formula (5) above, R9 to R11 each independently represent an optionally substituted alkyl group or an optionally substituted aryl group. [5] A polymerizable composition comprising the catalyst solution according to any one of [1] to [4], and a norbornene-based monomer as a polymerizable monomer. Effects of the Invention The present invention provides a catalyst solution which has high storage stability and demonstrates high catalytic activity even after long-term storage, and a polymerizable composition prepared using such a catalyst solution. DESCRIPTION OF EMBODIMENTS <Catalyst Solution> The catalyst solution according to the present invention is a catalyst solution comprising a metathesis polymerization catalyst, a coordinating compound containing a phosphorus atom, and a solvent, wherein the metathesis polymerization catalyst is a ruthenium-carbene complex represented by General Formula (1) or (2) described later, andthe coordinating compound containing a phosphorus atom is contained in an amount such that 6 to 1000 mol of phosphorus atoms are contained relative to 1 mol