Top > Search of International Patents > LIVING RADICAL POLYMERIZATION METHOD

LIVING RADICAL POLYMERIZATION METHOD

Foreign code F180009660
File No. 2900
Posted date Nov 21, 2018
Country WIPO
International application number 2011JP005180
International publication number WO 2012035769
Date of international filing Sep 14, 2011
Date of international publication Mar 22, 2012
Priority data
  • P2010-210156 (Sep 17, 2010) JP
Title LIVING RADICAL POLYMERIZATION METHOD
Abstract Provided is a living radical polymerization method that is inexpensive, has high activity, is environmentally superior, and does not require a radical initiator. Living radical polymerization can be performed without using a catalyst by controlling the amount of oxygen in the gas phase of a reactor to within an appropriate range. It is possible to obtain a polymer having a narrow molecular weight distribution and to dramatically reduce the cost of the living radical polymer by subjecting monomers having radical-reactive unsaturated bonds to radical polymerization. The present invention eliminates the harmful effects of conventional catalysts, such as toxicity, low solubility, discoloration and odor, and is exceptionally superior, environmentally and economically, to conventional living radical polymerization methods.
Outline of related art and contending technology BACKGROUND ART
Conventionally, a method for obtaining the vinyl polymer is a vinyl monomer, radical polymerization method was well known. Radical polymerization methods generally, of a vinyl polymer obtained is difficult to control the molecular weight is a drawback. In addition, that a vinyl polymer obtained, having various molecular weights which would cause the mixture of compounds, the vinyl polymer is a narrow molecular weight distribution in a problem that it is difficult to obtain the. More specifically, to control the reaction, weight average molecular weight (Mw) molecule and a number average molecular weight (Mw/Mn) as the ratio of (Mn), only to such an extent that 2-3 could not be reduced.
As a method to resolve such a drawback, from circa 1990, the living radical polymerization method has been developed. That is, according to the living radical polymerization method, and the molecular weight can be controlled, and a narrow molecular weight distribution in the polymer can be obtained. Specifically, Mw/Mn is less than or equal to 2 it is possible to easily obtain, such as state of the art used in the fields of nanotechnology as a method of manufacturing the polymer is being spotlighted.
In the radical polymerization method, a substance that inhibits oxygen radical reaction known as (polymerization inhibitor). Therefore, in general, the presence of oxygen by the reaction is carried out under an atmosphere which does not. Also in the living radical polymerization, in general, an inert gas such as nitrogen gas or argon atmosphere in the reaction vessel was replaced with the polymerization reaction has been carried out. That is, in order to carry out living radical polymerization reactions, oxygen in the atmosphere is eliminated as much as possible has been considered to be preferred. Oxygen can be used to actively living radical polymerization is one skilled in the art and have been considered. Even more, by controlling the concentration or amount of oxygen, living radical polymerization can be controlled in an entirely unexpected was to those skilled in the art.
Then, in order to control the living radical polymerization, conventional, control the progress of polymerization reaction can be added to the reaction compound as a catalyst has been considered necessary. Therefore, a compound that serves as catalyst was added to the reaction to control the living radical polymerization are in the prior art. That is, in the conventional living radical polymerization methods, in an atmosphere of an inert gas, a catalyst is added to the reaction method of controlling a polymerization is performed.
Is currently used as a catalyst in the living radical polymerization method, the transition metal complex-based catalyst has been known.
The transition metal complex catalysts are, for example, cu, Ni, Re, Rh, Ru compound such as a central metal and the ligand is coordinated to a complex is used. Such catalysts may be, for example, the following are described in the literature.
Patent Document 1 (Japanese Patent Application JP-2002-249505) is, cu, Ru, Fe, Ni complex such as a central metal and used as a catalyst is disclosed.
Patent Document 2 (Japanese Patent Application JP-11-322822) is, hydrido rhenium complex catalyst to be used as disclosed.
Non-patent document 1 is (Journal of The American Chemical Society 119,674-680 (1997)), 4, 4 '- di - (5 - nonyl) - 2, 2' - bipyridine is coordinated to a copper bromide compound used as a catalyst is disclosed.
However, such a transition metal complex catalyst is used, a large amount of transition metal complex catalyst used in an amount that is necessary and, after the reaction product from the large amount of catalyst used is not easy to completely remove the drawback. The catalyst which has become unnecessary when discarding the environmental problems can occur a drawback. Further, many of the transition metal can be toxic, the toxicity of the product remaining in the catalyst and is sometimes a problem on the environment, a transition metal food packaging, biological, medical materials or the like was difficult to use. In addition, after the reaction of the catalyst removed from a product environmental toxicity was a problem. Further, the transition metal remaining in the conductive polymer and the polymer is a possibility that has electrical conductivity, resist or an organic EL, fuel cell, solar cell, electronic materials such as lithium ion batteries used is also a problem that it is difficult. In addition, is not to form a complex is not dissolved in the reaction, a compound that serves as the ligand must be used and, for this purpose, production cost is increased, and, based on the total weight of the catalyst used is also a problem that further increases. Further, the ligand is, usually, expensive, complicated or also a problem that a required for the synthesis. In addition, high temperature polymerization reaction (for example, 110 °C or more) a drawback is required (for example, the non-patent document 1 is, the polymerization is performed in 110 °C).
In addition, the catalyst is not necessary to use the living radical polymerization methods are also known. For example, nitroxyl system, method and system of the known dithioesters. However, in these methods, a special protecting group introduced in the polymer growth is necessary, the protecting group is a disadvantage in that the very expensive. In addition, a high temperature (for example, 110 °C or more) polymerization reaction when it is necessary to be scattered. Further, it is not preferable polymer which generates a disadvantage to having performance. That is, the polymer is a polymer different from the original color of the colored easily in that, in addition, having the odor polymer which generates a disadvantage in that the-sensitive.
On the other hand, non-patent document 2 (Polymer Preprints 2005, 46 (2), 245-246) and Patent Document 3 (Japanese Patent Application JP-2007-92014) is, Ge, Sn compound such as a central metal and used as a catalyst is disclosed. Patent Document 4 (International Publication WO2008/139980 Publication) is, as a central metal and nitrogen or phosphorus compound used as a catalyst is disclosed. Non-patent document 3 (Polymer Preprints 2007, 56 (2), 2452 by The Society, edited by 56 times the first polymer discussion) compound as a central metal and phosphorus is used as a catalyst is disclosed.
Non-patent document 1 has been described in the copper complex catalyst, when polymerizing the polymer 1 kg the cost of the need for a catalyst is not limited to approximately several thousand yen. On the other hand, germanium in the catalyst, about a thousand yen to costs are reduced since, non-patent document 2 and patent document 3 aspect of the present invention, significantly reduce the cost of the catalyst was. However, the living radical polymerization is for application to general-purpose resin products and the like, has been a demand for further low cost. Non-patent document 3 and patent document 4 aspect of the present invention, the cost of the catalyst was further reduced.
However, Patent Document 1-4, and non-patent document 1-3 is, in the catalyst is not used to control the living radical polymerization method of obtaining a narrow molecular weight distribution of the polymer is not described.
In this way, in the prior art, halogen in inexpensive and general protecting group in the case of using, dormant species in order to generate radicals from a reversible compound or as a catalyst was added to the reaction and an absolute requirement has been considered. Is living radical polymerization, reversible radicals from dormant species can be generated since the basic principle and the, radical generation from the dormant species reversibly compounds that would have to be added to the reaction to control the reaction occurring on the premise of the course has been considered in some cases. That is, low cost and general halogen such as in the case where the protecting group is used, living radical polymerization without the addition of a catalyst cannot be performed to accomplish the above common technical knowledge. In the aforementioned Patent Document 1-4 and Non-Patent Document 1-3 is, both, based on the knowledge such techniques described.
Scope of claims (In Japanese)請求の範囲 [請求項1]
 リビングラジカル重合方法であって、
 ラジカル反応性モノマー、ラジカル開始剤、および炭素-ハロゲン結合を有する有機ハロゲン化物を含む反応液を反応容器に入れて重合を行う工程を包含し、
 ここで、重合工程における、反応容器中の液相の体積1mlあたりの該反応容器中の気相の酸素の量が1~70ミリモルである、方法。

[請求項2]
 請求項1に記載の方法であって、重合工程の際に、反応容器中の液相の体積1mlあたりの反応容器中の気相中の酸素の量が1.5~30ミリモルである、方法。

[請求項3]
 請求項1に記載の方法であって、前記重合の際に、ドーマント種からラジカルを可逆的に発生させるための触媒またはドーマント種からラジカルを可逆的に発生させるための触媒を反応液中に生成させるための化合物として、気体の酸素以外の化合物が添加されない、方法。

[請求項4]
 請求項1に記載の方法であって、前記容器の気相中の酸素濃度が1体積%~10体積%である、方法。

[請求項5]
 請求項1に記載の方法であって、前記容器の気相が、空気である、方法。

[請求項6]
 請求項1に記載の方法であって、前記有機ハロゲン化物中のハロゲンが結合している炭素原子に、2つのメチル基が結合しているか、または1つのメチル基および1つの水素が結合している、方法。

[請求項7]
 請求項1に記載の方法であって、前記有機ハロゲン化物中のハロゲンがヨウ素である、方法。

[請求項8]
 請求項1に記載の方法であって、ラジカル反応性モノマーが、アクリル酸、アクリレート、メタクリル酸、メタクリレートまたはスチレンである、方法。

[請求項9]
 請求項1に記載の方法であって、
 反応液に溶媒が使用されていないか、または、使用される溶媒の量が、前記モノマー100重量部に対して120重量部以下であり、
 前記ラジカル開始剤の濃度が、5~150mMであり、
 前記有機ハロゲン化物の濃度が、10~100mMである、
方法。

[請求項10]
 ポリマーの製造方法であって、
ラジカル反応性モノマー、ラジカル開始剤、および炭素-ハロゲン結合を有する有機ハロゲン化物を含む反応液を反応容器に入れて重合を行う工程を包含し、
 ここで、重合工程における、反応容器中の液相の体積1mlあたりの該反応容器中の気相の酸素の量が1~70ミリモルである、
製造方法。






  • Applicant
  • ※All designated countries except for US in the data before July 2012
  • Kyoto University
  • Inventor
  • GOTO, Atsushi
  • TSUJII, Yoshinobu
  • NAKAMURA, Kenichi
  • KAWAI, Michihiro
IPC(International Patent Classification)
Specified countries National States: AE AG AL AM AO AT AU AZ BA BB BG BH BR BW BY BZ CA CH CL CN CO CR CU CZ DE DK DM DO DZ EC EE EG ES FI GB GD GE GH GM GT HN HR HU ID IL IN IS KE KG KM KN KP KR KZ LA LC LK LR LS LT LU LY MA MD ME MG MK MN MW MX MY MZ NA NG NI NO NZ OM PE PG PH PL PT QA RO RS RU RW SC SD SE SG SK SL SM ST SV SY TH TJ TM TN TR TT TZ UA UG US UZ VC VN ZA ZM ZW
ARIPO: BW GH GM KE LR LS MW MZ NA SD SL SZ TZ UG ZM ZW
EAPO: AM AZ BY KG KZ MD RU TJ TM
EPO: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
OAPI: BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG
Please contact us by e-mail or facsimile if you have any interests on this patent. Thanks.

PAGE TOP

close
close
close
close
close
close