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Polymer-supported metal cluster composition 実績あり

外国特許コード F110003805
整理番号 E07603WO
掲載日 2011年7月5日
出願国 アメリカ合衆国
出願番号 59020605
公報番号 20080058200
公報番号 8110519
出願日 平成17年3月7日(2005.3.7)
公報発行日 平成20年3月6日(2008.3.6)
公報発行日 平成24年2月7日(2012.2.7)
国際出願番号 JP2005003848
国際公開番号 WO2005085307
国際出願日 平成17年3月7日(2005.3.7)
国際公開日 平成17年9月15日(2005.9.15)
優先権データ
  • 特願2004-064520 (2004.3.8) JP
  • 2005WO-JP03848 (2005.3.7) WO
発明の名称 (英語) Polymer-supported metal cluster composition 実績あり
発明の概要(英語) (US8110519)
The objective is to present compositions obtained by supporting by polymers micro clusters of transition metals and the like that are useful as catalysts in various reactions and, once used, are readily recovered and reused.
A polymer-supported metal cluster composition is obtained by supporting a transition metal by a cross-linked polymer, and the polymer-supported cluster composition is characterized by the cross-linked polymer obtained by cross-linking of a cross-linkable polymer containing a hydrophilic side chain and a hydrophobic side chain group having a cross-linkable functional group.
This polymer-supported metal cluster composition is, for example, preferably formed by first forming a micelle composed of the metal clusters supported by the cross-linkable polymer in a suitable solution and subsequently subjecting the cross-linkable polymer to a cross-linking reaction.
The composition is useful as a catalyst and the like in hydrogenation reactions, dehydrogenation reactions, allylic substitution reactions, oxidation reactions, coupling reactions and carbonylation reactions.
特許請求の範囲(英語) [claim1]
1. A polymer-supported metal cluster composition comprising a transition metal and a cross-linked polymer, wherein the transition metal is supported by the cross-linked polymer and the cross-linked polymer is obtained by cross-linking a cross-linkable polymer wherein the cross-linkable polymer contains at least one hydrophobic side chain and at least one hydrophilic side chain, wherein at least one hydrophilic side chain has a cross-linkable functional group, and wherein each hydrophobic side chain is free of hydrophilic substituents and cross-linkable functional groups, and wherein the composition is prepared, in a solution, by forming a micelle wherein clusters of the metal are supported by the cross-linkable polymer and then cross-linking the cross-linkable polymer.
[claim2]
2. The composition as in claim 1, wherein the cross-linkable polymer contains a hydrophobic side chain containing an aromatic group, and the micelle is formed by supporting a transition metal by the cross-linkable polymer using a ligand exchange reaction between a transition metal chelate and the aromatic group of the cross-linkable polymer.
[claim3]
3. The composition as in claim 1, wherein the metal clusters are 20 nm or smaller in diameter.
[claim4]
4. The composition as in claim 1, wherein the transition metal is at least one selected from the group consisting of palladium, cobalt, nickel, rhodium, ruthenium, iridium, gold and platinum.
[claim5]
5. The composition as in claim 1, wherein the transition metal is at least one selected from the group consisting of palladium, ruthenium, iridium, gold and platinum.
[claim6]
6. The composition as in claim 1, wherein the transition metal has zero valence.
[claim7]
7. The composition as in claim 1, wherein the cross-linkable polymer contains a hydrophilic side chain having an epoxy group, a carboxyl group, an isocyanate group or a thioisocyanate group.
[claim8]
8. The composition as in claim 7, wherein the cross-linkable polymer further contains at least one type of a hydrophilic side chain having a hydroxyl group, a primary or secondary amino group, or a thiol group.
[claim9]
9. The composition as in claim 1, wherein the cross-linkable polymer is: (i) a polymer or a copolymer obtained by polymerizing or copolymerizing at least one type of A1) monomer having an aromatic group as a hydrophobic side chain, a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond; or (ii) a copolymer obtained by copolymerizing at least two types of monomers selected from the group consisting of B1) monomer, B2) monomer, and B3) monomer, wherein the B1) monomer is a monomer having an aromatic group as a hydrophobic side chain, a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond, the B2) monomer is a monomer having an aromatic group as a hydrophobic side chain and a polymerizable double bond, and the B3) monomer is a monomer containing a hydrophilic side chain having a cross-linkable functional group and a polymerizable double bond.
[claim10]
10. The composition as in claim 9, wherein the cross-linkable polymer is a copolymer obtained by copolymerizing at least two types of monomers selected from B1) monomer, B2) monomer, and B3) monomer, wherein the B1) monomer is a monomer represented by chemical formula 1:

wherein R1 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), R2 is an aryl group having 6-14 carbon atoms, R3 is a covalent bond, an alkylene group having 1-6 carbon atom(s), -- R9(OR10)m -- , -- R9(COOR10)n -- or R9(COOR10)o(OR10)p -- , wherein R9 is independently a covalent bond or an alkylene group having 1-6 carbon atom(s), R10 is independently an alkylene group having 2-4 carbon atoms, m, n and p are integers of 1-10 and o is 1 or 2,
R4 is a carboxyl group, an isocyanate group, an isothiocyanate group, a hydroxyl group, a primary or secondary amino group, a thiol group or a group represented by chemical formula 2:

or chemical formula 3:

wherein R5 is independently an alkylene group having 1-6 carbon atom(s), R6 and R7 are each independently a hydrogen atom or an alkyl group having 1-6 carbon atom(s), and R6 may form a 3-6 membered ring with R5 or R7,
the B2) monomer is a monomer represented by chemical formula 4:

wherein R1 and R2 are independently as defined above, R11 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), and the B3) monomer is a monomer represented by chemical formula 5:

wherein R1, R3, R4 and R11 are independently as defined above.
[claim11]
11. A method for performing a hydrogenation reaction, a dehydrogenation reaction, an oxidation reaction, an allylic substitution reaction, a coupling reaction or a carbonylation reaction, wherein the method comprises catalyzing the reaction with a composition of claim 1.
[claim12]
12. The composition as in claim 9, wherein the cross-linkable polymer is a polymer obtained by polymerizing one type of A1) monomer represented by chemical formula 1:

wherein R1 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), R2 is an aryl group having 6-14 carbon atoms, R3 is a covalent bond, an alkylene group having 1-6 carbon atom(s), -- R9(OR10)m -- , -- R9(COOR10)n -- or R9(COOR10)o(OR10)p -- , wherein R9 is independently a covalent bond or an alkylene group having 1-6 carbon atom(s), R10 is independently an alkylene group having 2-4 carbon atoms, m, n and p are integers of 1-10 and o is 1or 2,
R4 is a carboxyl group, an isocyanate group, an isothiocyanate group, a hydroxyl group, a primary or secondary amino group, a thiol group or a group represented by chemical formula 2:

or chemical formula 3:

wherein R5 is independently an alkylene group having 1-6 carbon atom(s), R6 and R7 are each independently a hydrogen atom or an alkyl group having 1-6 carbon atom(s), and R6 may form a 3-6 membered ring with R5 or R7.
  • 発明者/出願人(英語)
  • KOBAYASHI SHU
  • OKAMOTO KUNIAKI
  • AKIYAMA RYO
  • OHNO KEIJI
  • INAGAKI YOSHIO
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
参考情報 (研究プロジェクト等) ERATO KOBAYASHI Highly Functionalized Reaction Environments AREA
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