US-20260125501-A1 - POLYMERIZABLE COMPOSITION AND NORBORNENE RESIN

US20260125501A1US 20260125501 A1US20260125501 A1US 20260125501A1US-20260125501-A1

Abstract

Provided is a polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordinating compound containing a phosphorus atom, 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 170 to 2000 mol of phosphorus atoms are contained relative to 1 mol of ruthenium atoms in the meta thesis polymerization catalyst.

Inventors

Masaki Takeuchi
Atsushi Hara

Assignees

RIMTEC CORPORATION

Dates

Publication Date: 20260507
Application Date: 20231011
Priority Date: 20221020

Claims (6)

1 . A polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordinating compound containing a phosphorus atom, 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 170 to 2000 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 . The polymerizable composition 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 Formula (3) and (4) above, R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 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.
3 . The polymerizable composition according to claim 1 , wherein the phosphines are an optionally substituted trialkylphosphine.
4 . The polymerizable composition 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, or R 9 to R 11 form a polyphosphine formed via an alkylene group.
5 . The polymerizable composition according to claim 1 , wherein the polymerizable composition comprises two or more preparative liquid formulations each of which alone does not cause a polymerization reaction, and the preparative liquid formulations, when mixed are capable of forming the polymerizable composition.
6 . A norbornene-based resin prepared through bulk polymerization of the polymerizable composition according to claim 1 .

Description

TECHNICAL FIELD The present invention relates to a polymerizable composition which has a curing time controlled within a proper range and can provide excellent workability, and a norbornene-based resin obtained using such a polymerizable composition. 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 polymerizable composition obtained using a ruthenium-carbene complex as a polymerization catalyst disclosed in Patent Document 1 has problems of short curing time and inferior workability when a metal mold is filled with the composition, for example. RELATED ART DOCUMENT Patent Document Patent Document 1: JP 2001-139668 A SUMMARY OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a polymerizable composition which has a curing time controlled within a proper range and can provide excellent workability. Means for Solving Problems The present inventor, who has conducted research to achieve the above object, has found that when a specific amount of a coordinating compound containing a phosphorus atom is added to a polymerizable composition comprising a norbornene-based monomer and a ruthenium-carbene complex containing phosphines as specific ligands as a metathesis polymerization catalyst, a polymerizable composition which has a curing time controlled within a proper range and can provide excellent workability can be obtained. This finding has led to the present invention. Specifically, the present invention provides the following: [1] A polymerizable composition comprising a norbornene-based monomer, a metathesis polymerization catalyst, and a coordinating compound containing a phosphorus atom,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 170 to 2000 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 L1 and L2 is phosphines.[2] The polymerizable composition according to [1], wherein L′ 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 polymerizable composition according to [1] or [2], wherein the phosphines are an optionally substituted trialkylphosphine.[4] The polymerizable composition according to any one of [1] to [3], wherein the coordinating compound containing a 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, or Re to Ru form a polyphosphine formed via an alkylene group.[5] The polymerizable composition according to any one of [1] to [4],wherein the polymerizable composition comprises two or more preparative liquid formulations each of which alone does not cause a polymerization reaction, and the preparative liquid formulations, when mixed, are capable of forming the polymerizable composition.[6] A norbornene-based resin prepared through bulk polymerization of the polymerizable composition according to any one of [1] to [5]. Effects of the Invention The present invention provides a polymerizable composition which has a curing time controlled within a proper range and can provide excellent workability, and a norbornene-based resin obtained by using such a polymerizable composition. DESCRIPTION OF EMBODIMENTS <Polymerizable Composition> The polymerizable composition according to th