Kyoto University

Chisso Corporation

Dainichiseika Color & Chemicals Mfg. Co., Ltd.

Jnc Corporation

Chisso Petrochemical Corporation

Fukuda Metal Foil & Powder Co., Ltd.

Takeshi Fukuda

Yoshinobu Tsujii

Atsushi Goto

Kohji Ohno

Mikio Yamahiro

Nobumasa Ootake

Hisao Oikawa

Kenichi Watanabe

Kenya Ito

Masami Tanaka

Yasuhiro Yamamoto

Yoshikazu Murakami

Hiroyuki Shimanaka

Kazuhiro Yoshida

Toshiyuki Hitotsuyanagi

Shinya Tsuchida

Koji Ohguma

Sachio Yoshikawa

Kensuke Hidaka

Naoyuki Sakai

Motonori Nishida

Taiyo Aoyagi

Yoshio Kohira

Jeong Sik Kim

Tamiho Mizutani

Provided is a low-cost, highly active, environmentally friendly living radical polymerization catalyst which does not require a radical initiator. An organic compound having an oxidation-reduction capability is used as a catalyst. Even if a radical initiator is not used, a monomer can be subjected to a radical polymerization to obtain a polymer having narrow molecular weight distribution. The cost of the living radical polymerization can be remarkably reduced. It is made possible to prevent adverse effects of using a radical initiator. 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), etc.

Catalyst for living radical polymerization and polymerization method

A highly active and environment-friendly catalyst for use in a living radical polymerization is provided. A catalyst for use in a living radical polymerization method is provided. The catalyst comprises a central element, which is selected from nitrogen and phosphorus, and at least one halogen atom, which is bound to the central element. A monomer having a radical reactive unsaturated bond is subjected to a radical polymerization reaction in the presence of the catalyst, thereby it is possible to obtain a polymer having narrow molecular weight distribution. The present invention has the merits such as low toxicity of the catalyst, a small amount of the catalyst being required, high solubility of the catalyst in the polymerization media, mild reaction conditions, no coloration, no odor (unnecessary post-treatment of molded products). The method of the present invention is more environment-friendly and economical than other living radical polymerization methods.

Living radical polymerization method using a phosphorus compound or nitrogen compound as a catalyst

Disclosed are an aqueous pigment dispersion containing at least a pigment, water, a high-molecular dispersant, and an alkali. The high-molecular dispersant is a diblock polymer having a formula (1) of A-B or a triblock polymer having a formula (2) of A-B-C. The diblock or triblock polymer is a diblock or triblock polymer obtained by polymerizing addition-polymerizable monomers with a radical generator while using an organic iodide as a polymerization initiating compound and an organic phosphorus compound, organic nitrogen compound or organic oxygen compound as a catalyst. Also disclosed are a production method and use of the aqueous pigment dispersion. With the high-molecular dispersant obtained by a simple living radical polymerization process free of the problems of conventional living radical polymerization and having a precisely-controlled molecular structure, the aqueous pigment dispersion can be obtained with the pigment dispersed in it.

Process for producing block polymer, coated pigment and aqueous pigment dispersion

Disclosed is a pigment dispersion containing at least a pigment, a liquid medium and a high-molecular dispersant. The high-molecular dispersant is a block polymer represented by A-B or A-B-C, in which A, B and C each represent a polymer block and the A and C blocks may be the same or different. The block polymer and its production process are also disclosed. The high-molecular dispersant is free of problems of a smell, coloration, a heavy metal and cost, and its use can provide a pigment dispersion excellent in the dispersion stability of a pigment.

Pigment dispersions

Provided is a method of living radical polymerization which does not necessitate complicated and intricate synthesis of a dormant species and which is highly efficient. A halogenated derivative compound is used as a dormant species for initiating living radical polymerization. The derivative compound is obtained by halogenating an alcohol compound having a non-conjugated structure or an amine compound having a non-conjugated structure with a halogenating agent capable of halogenating an alcohol or amine. A radical produced by elimination of halogen from the halogenated derivative compound is allowed to react with the unsaturated bond of the monomer. Thus, the monomer, which has a radical-reactive unsaturated bond, is polymerized by living radical polymerization. Preferably, the halogenating agent is a compound (NIS or the like) which also has a function as a catalyst.

Polymerization initiator for living radical polymerization

Provided is a catalyst used for a living radical polymerization method, which contains a central element consisting of carbon and at least one halogen atom binding to the central element. Further, a hydrocarbon compound can be used as a catalyst precursor. A monomer having a radical-reactive unsaturated bond is subjected to a radical polymerization reaction in the presence of the catalyst, consequently a polymer having narrow molecular weight distribution can be obtained, and thus 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 such as low toxicity of the catalyst, low amount of the catalyst used, high solubility of the catalyst, mild reaction conditions, and no coloration/no odor (no need of any post-treatments for a molded article), and the like.

Catalyst for living radical polymerization

Disclosed are a production process of a dye polymer having a dye content of from 1 to 50 wt %, and the dye polymer and its use. The production process includes subjecting an addition-polymerizable monomer to living radical polymerization by using, as a polymerization initiator, a dye having a polymerization initiating group enabling the living radical polymerization. The dye polymer and a composition of the dye polymer and a pigment are useful as good coloring agents for various products or articles. The colored products or articles are high in transparency, and are provided with high added value. The dye polymer can also be used as a dispersant for pigments, thereby making it possible to afford pigment dispersions excellent in dispersion properties and dispersion stability.

Method for producing dye polymer, dye polymer and use of the same

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.

Living radical polymerization method using alcohol as catalyst

A polymer represented by Formula (7): wherein all variables are defined in the specification, including Pwhich is a polymer chain obtained by polymerizing an addition-polymerizable monomer, which makes it possible to control the structure of the polymer as a molecular aggregate.

Polymer obtained by addition-polymerization initiated by a silicon compound

The present invention provides a silicon compound represented by Formula (1) and a polymer obtained by using the same, and this makes it possible not only to obtain an organic-inorganic composite material having a distinct structure but also to control the structure of the above polymer as a molecular aggregate. wherein Ris a group independently selected from hydrogen, alkyl having a carbon atom number of 1 to 40, substituted or non-substituted aryl and substituted or non-substituted arylalkyl; in this alkyl having a carbon atom number of 1 to 40, optional hydrogens may be substituted with fluorine, and optional &#x2014;CH&#x2014; may be substituted with &#x2014;O&#x2014;, &#x2014;CH&#x2550;CH&#x2014;, cycloalkylene or cycloalkenylene; in alkylene in this arylalkyl, optional hydrogens may be substituted with fluorine, and optional &#x2014;CH&#x2014; may be substituted with &#x2014;O&#x2014; or &#x2014;CH&#x2550;CH&#x2014;; and Ais a group having an &#x3b1;-haloester group.

Silicon compounds

A production process for a silicon compound represented by Formula (6), characterized by reacting a compound represented by Formula (4) with a compound represented by Formula (5): wherein all of the variables are defined in the specification.

Production process for a silicon compound

A highly active and environment-friendly catalyst for use in a living radical polymerization is provided. A catalyst for use in a living radical polymerization method is provided. The catalyst comprises a central element, which is selected from germanium, tin and antimony, and at least one halogen atom, which is bound to the central element. A monomer having a radical reactive unsaturated bond is subjected to a radical polymerization reaction under the presence of the catalyst, thereby it is possible to obtain a polymer having narrow molecular weight distribution. The present invention has the merits such as low toxicity of the catalyst, a small amount of the catalyst can be used, high solubility of the catalyst, mild reaction conditions, no coloration, no odor (unnecessary post-treatment of molded products). The method of the present invention is more environment-friendly and economical than a conventional living radical polymerization method.

Living radical polymerization method

A large part of conventional organic-inorganic composite materials is obtained by mechanical blending silsesquioxanes with organic polymers, and therefore it has been very difficult to control the structure thereof as the molecular aggregate of the composite materials. An object of the present invention is to provide a novel silicon compound having a living radical polymerization-initiating ability for an addition-polymerizable monomer and a polymer obtained using the same to thereby solve the problem described above regarding the conventional organic-inorganic composite materials. The present inventors have found that a novel silsesquioxane derivative to which a group having an ability to initiate polymerization of a monomer is useful as means for solving the problem described above. That is, the silsesquioxane derivative of the present invention is represented by Formula (1): wherein Ris hydrogen, alkyl, aryl or arylalkyl; Rand Rare alkyl, phenyl or cyclohexyl; and A is a group having an ability to initiate polymerization of a monomer.

Silicon compound

Since the majority of conventional organic/inorganic composite materials are obtained by mechanical blending of a silsesquioxane and an organic polymer or other means, it was extremely difficult to control the structure of the composite as a molecular agglomerate. In order to solve such a problem, the invention is to provide a silicon compound represented by Formula (1). This novel silicon compound has a living radical polymerization initiating ability for addition polymerizable monomers of a wide range. In Formula (1), Ris hydrogen, an alkyl, an aryl, or an arylalkyl; Ris an alkyl, phenyl, or cyclohexyl; and A is a group having a polymerization initiating ability for addition polymerizable monomers 

Organosilicon compound

A silicon compound represented by Formula (1). In Formula (1), Ris a group independently selected respectively from the group consisting of a hydrogen atom, alkyl, substituted or non-substituted aryl and substituted or non-substituted arylalkyl, and Ais an organic group substituted with a halogenated sulfonyl group and is preferably a group represented by Formula (2). In Formula (2), X is halogen; Ris alkyl; a is an integer of 0 to 2; and Zis a single bond or alkylene having a carbon number of 1 to 10.  The silicon compound provided by the present invention is a silsesquioxane derivative having an excellent living polymerizable radical polymerization initiating function. For example, it is possible to commence polymerization by allowing an acryl base monomer to coexist to form an acryl base polymer making use of one point of the structure of the silsesquioxane in the present invention as a starting point. Because a halogenated sulfonyl group has a strong electrophilicity, it is possible to synthesize various silsesquioxane derivatives by reacting the silicon compound provided by the present invention with various nucleophilic reagents, and it can actively be used as an intermediate useful for organic synthesis.

Growing community of inventors

Kyoto, Japan

Takeshi Fukuda