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Living radical polymerization method using alcohol as catalyst

外国特許コード F120006114
整理番号 S2008-0177
掲載日 2012年1月6日
出願国 アメリカ合衆国
出願番号 99183809
公報番号 20110124832
公報番号 8378044
出願日 平成21年2月6日(2009.2.6)
公報発行日 平成23年5月26日(2011.5.26)
公報発行日 平成25年2月19日(2013.2.19)
国際出願番号 JP2009052115
国際公開番号 WO2009136510
国際出願日 平成21年2月6日(2009.2.6)
国際公開日 平成21年11月12日(2009.11.12)
優先権データ
  • 特願2008-123817 (2008.5.9) JP
  • 2009JP052115 (2009.2.6) WO
発明の名称 (英語) Living radical polymerization method using alcohol as catalyst
発明の概要(英語) Provided is a low-cost, environmentally friendly living radical polymerization catalyst having high activity.
The catalyst is used for a living radical polymerization method, and contains a central element consisting of oxygen and at least one halogen atom bound to the central element.
Furthermore, an alcohol compound can be used as a catalyst precursor.
By polymerizing a monomer in the presence of the catalyst, a polymer having narrow molecular weight distribution can be obtained, and the cost of the living radical polymerization can be remarkably reduced.
The present invention is significantly more environmentally friendly and economically excellent than conventional living radical polymerization methods, due to advantages of the catalyst such as low toxicity of the catalyst, low amount of the catalyst necessary, high solubility of the catalyst, mild reaction conditions, and no coloration/no odor (which do not require a post-treatment for a molded article), and the like.
従来技術、競合技術の概要(英語) BACKGROUND ART
A radical polymerization method has been a well-known method for polymerizing vinyl monomers to obtain a vinyl polymer.
Generally, a radical polymerization method has the disadvantage of the difficulty in controlling the molecular weight of the obtained vinyl polymer.
Further, there is the disadvantage that the obtained vinyl polymer is a mixture of compounds having various molecular weights, and thus it is difficult to obtain a vinyl polymer having narrow molecular weight distribution.
Specifically, even if the reaction is controlled, the ratio of weight-average molecular weight (Mw) and number-average molecular weight (Ma), (Mw/Mn), can be only reduced to about 2 to 3.
As a method for eliminating the aforementioned disadvantages, since around 1990, a living radical polymerization method has been developed.
Specifically, according to the living radical polymerization method, it is possible to control the molecular weight.
It is also possible to obtain a polymer having narrow molecular weight distribution.
Specifically, a polymer having Mw/Mn of 2 or less can easily be obtained.
Therefore, this method has come into the limelight as a method for producing a polymer used in a high technology such as nanotechnology.
Catalysts which are currently used in living radical polymerization methods include transition metal complex-type catalysts.
For transition metal complex-type catalysts, complexes in which a ligand is coordinated to a compound having a central metal of Cu, Ni, Re, Rh, Ru, or the like have been used.
Such catalysts are described in the following documents for example.
Patent document 1 (Japanese Laid-open Publication No. 2002-249505) discloses that a complex with a central metal which is Cu, Ru, Fe, Ni or the like, and it is used as a catalyst.
It should be noted that Patent Document 1 describes in its claim 1 that an organic halide is used as a polymerization initiator.
This description is not intended to mean that a halogenated hydrocarbon acts as a catalyst for living radical polymerization.
According to the invention of Patent Document 1, a metal complex having a transition metal as the central metal is used as the catalyst for living radical polymerization.
According to the invention of Patent Document 1, an organic halide is used as a dormant species that will be described later in the present specification.
Patent document 2 (Japanese Laid-open Publication No. 11-322822) discloses that hydrido rhenium complex is used as a catalyst.
It should be noted that Patent Document 2 describes a "catalyst for radical living polymerization comprising a combination of a hydrido rhenium complex and a halogenated hydrocarbon" in claim 1.
This description is not intended to mean that a halogenated hydrocarbon acts as a catalyst for living radical polymerization.
According to the invention of Patent Document 2, the hydrido rhenium complex is used as the catalyst for living radical polymerization.
According to the invention of Patent Document 2, the halogenated hydrocarbon is used as a dormant species that will be described later in the present specification.
The combination of the catalyst and the dormant species is described as a catalyst in Patent Document 2, and this does not describe that the halogenated hydrocarbon serves as the catalyst for living radical polymerization.
Non-patent document 1 (Journal of The American Chemical Society 119:674-680 (1997)) discloses that a compound in which 4,4'-di-(5-nonyl)-2,2'-bipyridine is coordinated with copper bromide, is used as a catalyst.
It should be noted that Non-Patent Document 1 describes that 1-phenylethyl bromide was used at the time of polymerization of styrene.
That is, according to the invention of Patent Document 2, a copper bromide complex is used as a catalyst for living radical polymerization, and 1-phenylethyl bromide is used as the dormant species that will be described later in the present specification.
However, when such transition metal complex catalysts are used, it is necessary to use a large amount of the catalyst.
This is disadvantageous as it is not easy to completely remove the large amount of the catalyst used, from the products after the reaction.
Another disadvantage is environmental problems which may occur by the disposal of the catalyst.
The transition metal for the living radical polymerization method includes many toxic metals.
The disposal of a large amount of such toxic metals causes environmental problems.
Furthermore, there are cases where toxicities of catalysts remaining in products cause environmental problems.
Due to the toxicity, it is difficult to use the transition metal catalysts for the production of food packages, material for living body, and medical material.
Additionally, there is a problem associated with a high electroconductivity of the transition metal remaining in polymer, rendering the polymer conductive and hence unsuitable for use in electronic material such as resist material.
Furthermore, the transition metal-type catalysts do not dissolve in a reaction solution unless they form a complex.
Therefore, it is necessary to use a ligand as an additive to form a complex.
This causes problems, i.e., an increase of the cost of production and also an increase of the total weight of the catalyst used.
Further, a ligand is usually expensive and requires a complicated synthesis method.
Furthermore, the polymerization reaction requires a high temperature (for example, 110 deg. C. or higher). (For example, in aforementioned Non-patent document 1, the polymerization reaction is performed at 110 deg. C.).
It is noted that a living radical polymerization methods, which do not require a catalyst, have also been known.
For example, a nitroxyl-type method and dithioester-type method have been known.
However, these methods have the following disadvantages.
A special protecting group (i.e., a certain nitroxide or dithioester group) must be introduced to the polymer growing chain.
The protecting group is very expensive.
Further, the polymerization reaction requires a high temperature (for example, 100 deg. C. or higher).
Further, the produced polymer is likely to have undesirable properties.
For example, the produced polymer is likely to be colored differently from the natural color of the polymer.
Further, the produced polymer is likely to have an odor.
On the other hand, Non-Patent Document 2 (Polymer Preprints 2005, 46(2), 245-246) and Patent Document 3 (Japanese Laid-open Patent Publication No. 2007-92014) disclose that compounds having Ge, Sn and the like as central metals are used as catalysts.
In regard to the copper complex catalyst described in Non-Patent Document 1, the cost for the catalyst required to polymerize 1 kg of a polymer sums up to approximately several thousand yens.
On the other hand, in regard to a germanium catalyst, the cost is cut down to about one thousand yens.
Thus, the invention of Non-Patent Document 2 markedly decreases the cost for the catalyst.
However, in order to apply living radical polymerization to general-purpose resin products and the like, a further less expensive catalyst is demanded.
In general, it is known that transition metals or compounds of transition metal elements are preferable as catalysts for various chemical reactions.
For example, the following is described on page 311 of "Inorganic Chemistry" by J. D. LEE (Tokyo Kagaku Dojin, edition published on Apr. 15, 1982): "Many transition metals and the compounds of the transition metals have catalytic action . . . in some cases, a transition metal may adopt various valences and form unstable intermediate compounds, while in other cases, a transition metal provides good reaction surfaces, and these serve as catalytic actions." That is, it has been widely understood by those skilled in the art that the properties characteristic to transition metals, such as the ability to form various unstable intermediate compounds, are indispensable in connection with the function of a catalyst.
Furthermore, Ge, Sn and Sb described in Non-Patent Document 2 are not transition metals, but are elements that belong to the 4th period and the 5th period of the Periodic Table and have large atomic numbers and have a large number of electrons and a large number of electron orbitals.
Therefore, it is surmised in regard to Ge, Sn and Sb that the fact that these atoms have a large number of electrons and a large number of electron orbitals, works advantageously in terms of their action as catalysts.
According to such a common technological knowledge in connection with various catalysts of the prior art, it has been believed that the typical elements which belong to the 2nd period and the 3rd period of the Periodic Table, merely have a small number of electrons and a smaller number of electron orbitals, and thus it is disadvantageous to use them in a catalyst compound, and catalytic action cannot be expected from compounds utilizing these typical elements.
Furthermore, Non-patent document 3 discloses a catalyst using a phosphorus compound, but does not describe the use of oxygen, which has a different electron configuration and significantly different characteristics from phosphorus, as a central element.
[Patent document 1] Japanese Laid-open Patent Publication No. 2002-249505
[Patent document 2] Japanese Laid-open Patent Publication No. 11-322822
[Patent document 3] Japanese Laid-open Patent Publication No. 2007-92014
[Non-patent document 1] Journal of the American Chemical Society 119, 674-680 (1997)
[Non-patent document 2] Polymer Preprints 2005, 46(2), 245-246, "Germanium- and Tin-Catalyzed Living Radical Polymerizations of Styrene," American Chemical Society, Division of Polymer Chemistry
[Non-patent document 3] Polymer Preprints 2007, 56(2), 2452, "A Novel Living Radical Polymerization using Germanium and Phosphorus Compound," The Society of Polymer Science, Japan, 56th Symposium on Macromolecules

特許請求の範囲(英語) [claim1]
1. A method of conducting a living radical polymerization, comprising: reacting a radical generated from a radical initiator and a catalyst precursor compound to form an activated radical; and
polymerizing a monomer having a radical reactive unsaturated bond using the activated radical to obtain a polymer;
wherein the precursor compound comprises at least one hydroxyl group bonded to carbon, silicon, nitrogen, or phosphorus,
a radical generated from the radical initiator abstracts a hydrogen atom from the hydroxyl group in the precursor compound to form the activated radical, and
the activated radical acts as a living radical catalyst of the polymerization reaction of the monomer,
wherein an organic halide having a carbon-halogen bond is used in the living radical polymerization reaction, and a halogen given from the organic halide is used as a protecting group of a growing chain.
[claim2]
2. The method according to claim 1, wherein an atom bonded to the hydroxyl group is carbon.
[claim3]
3. The method according to claim 1, wherein the atom bonded to the hydroxyl group has a double bond or triple bond between the atom and an adjacent atom, and an activated radical formed after the hydrogen of the hydroxyl group is abstracted is stabilized by the resonance between the radical and the double bond or triple bond.
[claim4]
4. The method according to claim 1, wherein the catalyst precursor compound is alcohol or phenol represented by the formula (I):
R1n(OH)m (I)
wherein R1 is substituted or unsubstituted alkyl, alkenyl, or alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
n is a positive integer;
m is a positive integer;
wherein the substituent is alkyl, alkenyl, alkylcarboxyl, haloalkyl, alkylcarbonyl, amino, cyano, alkoxy, aryl, or alkyl-substituted aryl;
a carbon chain in R1 has a chain structure or cyclic structure; and
when R1 has a cyclic structure, the cyclic structure may be a fused cyclic structure in which one or more rings are fused to an aryl or heteroaryl ring, wherein one or more cyclic structures fused to the aryl or heteroaryl ring may be a heterocycle containing an oxygen or nitrogen atom as a heteroatom.
[claim5]
5. A catalyst for a living radical polymerization method, which consists of a compound comprising: at least one central element which is oxygen; a halogen atom bonded to the central element; and a carbon atom, silicon atom, nitrogen atom or phosphorus atom bonded to the central element.
[claim6]
6. The catalyst according to claim 5, wherein the central element is bonded to a halogen atom and a carbon atom.
[claim7]
7. The catalyst according to claim 5, wherein the catalyst has a structure in which an atom bonded to the central element has a double bond or triple bond between the atom and an adjacent atom, and an activated radical formed after the halogen atom bonded to the central element is eliminated is stabilized by the resonance between the radical and the double bond or triple bond.
[claim8]
8. The catalyst according to claim 5, which consists of a compound of the following general formula (Ia):
R1n(OX1)m (Ia)
wherein R1 is alkyl, alkylcarboxyl, haloalkyl, alkylcarbonyl, alkenyl, alkynyl, aryl, heteroaryl, substituted aryl, or substituted heteroaryl,
n is a positive integer;
m is a positive integer;
X1 is halogen.
[claim9]
9. The catalyst according to claim 5, wherein the halogen is iodine or bromine.
[claim10]
10. The catalyst according to claim 5, wherein the halogen is iodine.
[claim11]
11. A polymerization method comprising conducting a living radical polymerization, wherein the living radical polymerization step is conducted in the presence of the catalyst according to claim 5.
[claim12]
12. The method according to claim 1, wherein a concentration of the catalyst in a reaction solution is 0.75 wt % or less.
[claim13]
13. The method according to claim 1, wherein a reaction temperature is 20 to 100 deg. C.
[claim14]
14. The method according to claim 1, wherein two or three carbon atoms are bonded to the carbon atom to which the halogen in the organic halide is bonded.
  • 発明者/出願人(英語)
  • GOTO ATSUSHI
  • FUKUDA TAKESHI
  • TSUJII YOSHINOBU
  • KYOTO UNIVERSITY
国際特許分類(IPC)
米国特許分類/主・副
  • 526/204
  • 526/210
  • 526/348
  • 544/265
  • 549/400
  • 549/408
  • 558/423
  • 568/300
  • 568/379
  • 568/650
  • 568/706
  • 568/716
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