Method for producing ring-opening metathesis polymer hydride, and resin composition

Patent metadata

Field	Value
Publication number	US-9850325-B2
Application number	US-201314385582-A
Country	US
Kind code	B2
Filing date	Mar 14, 2013
Priority date	Mar 16, 2012
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

A method for producing a hydrogenated ring-opening metathesis polymer includes subjecting a cyclic olefin to ring-opening metathesis polymerization in the presence of a polymerization catalyst to produce a ring-opening metathesis polymer, and hydrogenating at least some of carbon-carbon double bonds of the ring-opening metathesis polymer, at least one ruthenium compound selected from a group made of a ruthenium compound represented by a formula (I), (II), (III), and (IV) being used as the polymerization catalyst; and a resin composition having a hydrogenated ring-opening metathesis polymer produced by this method. It is possible to industrially advantageously produce a hydrogenated ring-opening metathesis polymer that exhibits especially excellent light transmittance.

First claim

The invention claimed is:

1. A method for producing a hydrogenated ring-opening metathesis polymer comprising
subjecting a cyclic olefin to ring-opening metathesis polymerization in the presence of a polymerization catalyst to produce a ring-opening metathesis polymer, and hydrogenating at least some of carbon-carbon double bonds of the ring-opening metathesis polymer, the cyclic olefin comprising:
(i) a monomer represented by the following formula (2),

wherein
R 28 is a C 1 -C 20 alkyl group, a C 3 -C 20 cycloalkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, or a group represented by the following formula (3),

wherein
R 29 is a C 1 -C 3 alkylene group, and
R 30 and R 31 are independently a C 1 -C 10 alkyl group or a C 1 -C 10 alkyl halide group, and
(ii) a cyclic olefin that includes a protonic polar group, the proportion of the cyclic olefin including a protonic polar group being 10-90 mol % based on the total cyclic olefins, the polymerization catalyst being a ruthenium compound shown by the following formula (I),

wherein
X 1 and X 2 are independently a halogen atom;
L 1 represents a group represented by any of the following formulas (1-1) to (1-3),

wherein
R 17 and R 18 are independently a phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,4,6-trimethylphenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, or methylnaphthyl group,
R 19 to R 22 are independently a hydrogen atom or a C 1 -C 10 alkyl group, and
R 23 to R 25 are independently
a C 1 -C 20 alkyl group,
a C 1 -C 20 alkoxy group,
a C 3 -C 20 cycloalkyl group,
a C 6 -C 20 aryl group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 6 -C 20 aryloxy group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group, or
a C 2 -C 20 heterocyclic group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group;

R 0 is
a hydrogen atom,
a halogen atom,
a nitro group,
a cyano group,
a C 1 -C 20 alkyl group,
a C 1 -C 20 alkoxy group,
a C 1 -C 20 alkylthio group,
a tri-C 1 -C 20 alkylsilyl group,
a tri-C 1 -C 20 alkylsilyloxy group,
a C 6 -C 20 aryl group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 6 -C 20 aryloxy group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 2 -C 20 heterocyclic group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 1 -C 20 alkylsulfonyl group,
a C 1 -C 20 alkylsulfinyl group,
a formyl group,
a C 1 -C 20 alkylcarbonyl group,
a C 1 -C 20 alkoxycarbonyl group,
a di-C 1 -C 20 alkylcarbamoyl group,
a di-C 1 -C 20 alkylureido group, or
a di-C 1 -C 20 alkylsulfonylamino group;

R 1 is
a group represented by (R b1 )(R b2 )NSO 2 —,
a formyl group,
a C 1 -C 20 alkylcarbonyl group,
a C 1 -C 20 alkoxycarbonyl group,
a group represented by (R c1 )(R c2 )NCO—,
an amide group,
a halogen atom,
a di-C 1 -C 20 alkylureido group, or
a C 1 -C 20 alkylsulfonylamino group, wherein
R b1 and R c1 are
a hydrogen atom,
a C 1 -C 20 alkyl group, or
an aryl group, which may be substituted with a halogen atom a C 1 -C 6 alkyl group, C 1 -C 16 alkoxy group, a nitro group, or a cyano group, and

R b2 and R c2 are
a hydrogen atom,
a C 1 -C 20 alkyl group, or an aryl group, which may be substituted with a halogen atom a C 1 -C 6 alkyl group, C 1 -C 16 alkoxy group, a nitro group, or a cyano group,

provided that R b1 and R b2 or R c1 and R c2 optionally bond to each other to form a ring;
R 2 and R 3 are independently a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 1 -C 20 alkylthio group, a tri-C 1 -C 20 alkylsilyloxy group, a C 6 -C 20 aryloxy group, a C 6 -C 20 aryl group, a C 2 -C 20 heterocyclic group, a C 1 -C 20 alkoxycarbonyl group, a di-C 1 -C 20 alkylcarbamoyl group, a di-C 1 -C 20 alkylureido group, or a C 1 -C 20 alkylsulfonylamino group;
R 4 is
a hydrogen atom,
a C 1 -C 20 alkyl group,
a C 1 -C 20 alkoxy group,
a C 1 -C 20 alkylthio group,
a tri-C 1 -C 20 alkylsilyl group,
a tri-C 1 -C 20 alkylsilyloxy group,
a C 6 -C 20 aryl group, which may be substituted with a halogen atom, C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 6 -C 20 aryloxy group, which may be substituted with a halogen atom, C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group, a nitro group, or a cyano group, or
a C 2 -C 20 heterocyclic group, which may be substituted with a halogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a nitro group, or a cyano group,
a C 1 -C 20 alkylsulfonyl group,
a C 1 -C 20 alkylsulfinyl group,
a C 1 -C 20 alkylcarbonyl group,
a C 1 -C 20 alkoxycarbonyl group,
a di-C 1 -C 20 alkylcarbamoyl group,
a di-C 1 -C 20 alkylureido group,
a C 1 -C 20 alkylsulfonylamino group, or
a C 6 -C 20 arylcarbonyl group that is optionally substituted with a halogen atom; and

Y 1 is an oxygen atom, a sulfur atom, NR b , or PR b , where R b is a hydrogen atom or a C 1 -C 20 alkyl group; wherein
the reaction of polymerizing the cyclic olefin by ring-opening metathesis polymerization is conducted in the presence of the polymerization catalyst in an ether-based solvent wherein the ether-based solvent is present in an amount of 0.5-100 parts by weight per one part by weight of the cyclic olefin.

2. The method according to claim 1 , wherein at least 98% of the carbon-carbon double bonds of the ring-opening metathesis polymer are hydrogenated.

3. The method according to claim 1 , wherein the ruthenium compound represented by the formula (I) is a compound represented by a formula (I-2),

wherein L 1 , R 0 , R 2 to R 4 , R b1 , and R b2 are the same as defined in claim 1 .

4. The method according to claim 1 , wherein the ruthenium compound represented by the formula (I) is a compound represented by a formula (I-3),

wherein R 0 , R 2 to R 4 , R 17 , R 18 , R b1 , and R b2 are the same as defined in claim 1 .

5. The method according to claim 1 , wherein the ruthenium compound represented by the formula (I) is a compound represented by a formula (I-4),

wherein R 0 , R 2 to R 4 , R 23 to R 25 , R b1 , and R b2 are the same as defined in claim 1 .

6. A method according to claim 5 , wherein the metathesis polymerization of the cyclic olefin is conducted in the presence of the polymerization catalyst in an ether solvent by a solution polymerization.

7. The method according to claim 2 , wherein the ruthenium compound represented by

Assignees

• Zeon Corp

Inventors

• Tsutsumi Takashi
• Taguchi Kazunori
• Ohsaku Yumi

Classifications

• C08F8/04 Primary

  Reduction, e.g. hydrogenation · CPC title

• C08G2261/92

  TFT applications · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08G2261/95

  Use in organic luminescent diodes · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title