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Polymer-supported metal cluster compositions 実績あり

外国特許コード F110003944
整理番号 E07603WO
掲載日 2011年7月7日
出願国 欧州特許庁(EPO)
出願番号 05720120
公報番号 1739104
公報番号 1739104
出願日 平成17年3月7日(2005.3.7)
公報発行日 平成19年1月3日(2007.1.3)
公報発行日 平成26年7月9日(2014.7.9)
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
  • 2005JP003848 (2005.3.7) WO
  • 特願2004-064520 (2004.3.8) JP
発明の名称 (英語) Polymer-supported metal cluster compositions 実績あり
発明の概要(英語) 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 containing (i) a hydrophobic side chain that does not have a hydrophilic substituent or a cross-linkable functional group; and (ii) a hydrophilic side chain having a cross-linkable functional group,
wherein the cross-linkable polymer does not contain a hydrophobic side chain having hydrophilic substituents or cross-linkable functional groups; and
wherein each of the hydrophobic side chain that does not have a hydrophilic substituent or cross-linkable functional group, and the hydrophilic side chain containing a cross-linkable functional group, are directly bonded to a main polymer chain; 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; and
wherein the cross-linkable polymer is a copolymer obtained by allowing to copolymerize at least two monomers selected from: 1) a monomer containing a hydrophobic side chain that does not have a hydrophilic substituent or a cross-linkable functional group, a hydrophilic side chain containing a cross-linkable functional group and a polymerizable double bond; 2) a monomer containing a hydrophobic side chain that does not have a hydrophilic substituent or a cross-linkable functional group and a polymerizable double bond; and 3) a monomer containing a hydrophilic side chain containing a cross-linkable functional group and a polymerizable double bond, and wherein at least two different monomers of type (1) are contained; and wherein the monomer (1) is represented by the following chemical formula 1: (see diagramm) wherein R **1 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s), R **2 is an aryl group having 6-14 carbon atoms, R **3 is a covalent bond, an alkylene group having 1-6 carbon atom(s), -R **9(OR **10) m-, -R **9(COOR **10) n- or R **9 (COOR **10) o(OR **10) p-,
wherein R **9 is independently a covalent bond or an alkylene group having 1-6 carbon atom(s),
R **10 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,
R **4 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 the following chemical formula 2: (see diagramm) or a group represented by the following chemical formula 3: (see diagramm) wherein R **5 is independently an alkylene group having 1-6 carbon atom(s), R **6 and R **7 are each independently a hydrogen atom or an alkyl group having 1-6 carbon atom(s), and R **6 may form a 3-6 membered ring with R **5or R **7,
the monomer (2) is represented by the following chemical formula 4: (see diagramm) wherein R **1 and R **2 are independently as defined above, R **11 is a hydrogen atom or an alkyl group having 1-6 carbon atom(s),
and the monomer (3) is represented by the following chemical formula 5: (see diagramm) wherein R **1, R **3, R **4 and R **11 are independently as defined above.
[claim2]
2. The composition as in claim 1, wherein 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 groups of the cross-linkable polymer.
[claim3]
3. The composition as in claim 1 or claim 2, wherein the metal clusters are 20 nm or smaller in diameter.
[claim4]
4. The composition as in any preceding claim, wherein the transition metal is at least one selected from palladium, cobalt, nickel, rhodium, ruthenium, iridium, gold and platinum.
[claim5]
5. The composition as in claim 4, wherein the transition metal is at least one selected from palladium, ruthenium, iridium, gold and platinum.
[claim6]
6. The composition as in any preceding claim, wherein the transition metal has zero valence.
[claim7]
7. The composition as in any preceding claim, 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 hydrophobic side chain that does not have a hydrophilic substituent or a cross-linkable functional group contains an aromatic group.
[claim10]
10. Use of the composition as in any of claims 1-9 for a catalyst in a hydrogenation reaction, a dehydrogenation reaction, an oxidation reaction, an allylic substitution reaction, a coupling reaction or a carbonylation reaction.
  • 出願人(英語)
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • 発明者(英語)
  • KOBAYASHI SHU
  • OKAMOTO KUNIAKI
  • AKIYAMA RYO
  • OHNO KEIJI
  • INAGAKI YOSHIO
国際特許分類(IPC)
欧州特許分類/主・副
  • B01J031/16D
  • C07C017/14
  • C07C045/68
  • C07C049/796
  • C07C067/31
  • C07C067/343
  • C08F212/08
  • C08F212/14
  • L01J231/42B10
  • L01J231/64B2
  • L01J531/82F
  • L01J531/82J
  • L01J531/82L
指定国 Contracting States: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR
参考情報 (研究プロジェクト等) ERATO KOBAYASHI Highly Functionalized Reaction Environments AREA
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