JP2007231292A - Method for producing star-shaped polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a star-shaped polymer, and to provide an improved method. <P>SOLUTION: This method for producing a star-shaped vinylic polymer, comprising performing the atom-moving radical polymerization of a vinylic monomer and then adding a compound (a) having two or more polymerizable carbon-carbon double bonds at a time near to the finish point of the polymerization, is characterized by using a reaction catalyst of transition metal complex in an amount of ≥0.5 mole equivalent, preferably ≥1 mole equivalent, based on an initiator. In addition, a method for further adding the catalyst is also disclosed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for producing a vinyl polymer having a star-shaped structure.

A star polymer is a polymer in which a linear arm is radially extended from a central portion, and is known to have various properties different from those of a linear polymer. There are roughly two types of methods for synthesizing star polymers. One is a method of growing a polymer as an arm from a central compound or polymer, and the other is a method in which a polymer as an arm is first formed and connected to form a star. Examples of the method of connecting the arms include a method of reacting with a compound having a plurality of functional groups that react with a terminal functional group, and a method of adding a compound having a plurality of polymerizable groups after polymerization of the arms.

As the polymer constituting such a star polymer, there are both homopolymers and copolymers, and there are various types such as polystyrene, poly (meth) acrylate, polydiene, polyether, polyester, polysiloxane and the like. . In order to obtain a controlled star structure, anionic polymerization, living cationic polymerization or condensation polymerization is often used because polymerization must be controlled in any method.

Among the polymers obtained by ionic polymerization or condensation polymerization exemplified above, vinyl polymers obtained by radical polymerization and having a star-shaped structure have not been practically used yet. Among them, a method for constructing a chain extension or a star structure by joining polymerization growth ends has not been successful. Among vinyl polymers, (meth) acrylic polymers have characteristics that cannot be obtained with the above polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. Those having an alkenyl group or a crosslinkable silyl group in the side chain are used for highly weather-resistant paints. On the other hand, the polymerization control of the acrylic polymer is not easy due to the side reaction, and chain extension after polymerization or construction of a star structure is very difficult.

Recently, the inventors have extended the chain by polymerizing vinyl monomers in living radical polymerization and adding a compound (i) having two or more polymerizable carbon-carbon double bonds at the end of polymerization. The present inventors have found a method for producing a polymer or a star polymer.

In the present invention, an object of the present invention is to provide an improved method for producing the above star polymer.

The present invention relates to a transition metal catalyst (b) in a process for producing a polymer in which a compound (a) having two or more polymerizable carbon-carbon double bonds is added near the end point of atom transfer radical polymerization of a vinyl monomer. ) Is used in a total amount of 0.5 molar equivalents or more, preferably 1 molar equivalent or more with respect to the initiator.

The inventors produce a star-shaped vinyl polymer by adding a compound (a) having two or more polymerizable carbon-carbon double bonds in the vicinity of the polymerization end point of atom transfer radical polymerization of a vinyl monomer. It has been found that the amount of catalyst is important in the process.

In atom transfer radical polymerization, the polymerization reaction proceeds even when the amount of the catalyst is less than the growth terminal (so-called catalyst amount). That is, the polymerization can be controlled even with a smaller amount of catalyst than the growth terminal. However, when the radicals at the growing ends are coupled to each other, the catalyst becomes a complex having a higher oxidation number by the amount of the coupling, and the polymerization reaction is slowed down. In ordinary atom transfer radical polymerization systems, radical-radical coupling reactions do not occur so much, so this is not a problem. A ring reaction is likely to occur. Therefore, a certain amount of catalyst is required to some extent with respect to the growth end.

On the other hand, when the amount of the catalyst is increased, the polymerization rate tends to increase and the exotherm increases, so that the control of the polymerization tends to be difficult. In order to solve this problem and to achieve the object of the present invention, after adding a compound (i) having two or more polymerizable carbon-carbon double bonds, an additional catalyst (d) is used as zero valence. It is preferable to add copper, a transition metal compound, or a transition metal complex. Further, it is more preferable that the metal of the additional catalyst (d) has a smaller oxidation number than the metal of the transition metal compound (c) that has been used for the polymerization of the vinyl monomer.

The transition metal compound (c) and / or the transition metal of the additional catalyst (d) is not particularly limited, but copper, nickel, ruthenium and iron are preferable, and copper is particularly preferable. The additional catalyst (d) is preferably zero-valent copper or a complex of zero-valent copper.

The transition metal compound (c) of the present invention mainly means a polymerization reaction catalyst of a vinyl monomer, and in the present invention, a compound (i) having two or more polymerizable carbon-carbon double bonds is added. Previously added to the polymerization reaction system. Further, the additional catalyst (d) of the present invention is a compound (i) having two or more polymerizable carbon-carbon double bonds near the end point of the polymerization of the vinyl monomer using the transition metal compound (c). Is added to the reaction system after the addition of.

In the present invention, the term “transition metal catalyst (b)” is used to include both the transition metal compound (c) and the additional catalyst (d). The transition metal catalyst (b), the transition metal compound (c), and the additional catalyst (d) in the present invention may be the same compound or different from each other.

In the present invention, the compound (a) having two or more polymerizable carbon-carbon double bonds is preferably a compound represented by a chemical formula selected from the general formula 1, 2 or 3.

（上の式中、Ｒ^１はＰｈ、ＣＮ、ＣＯ_２Ｒ^３（Ｒ^３は一価の有機基）から選ばれる基であり、且つ、Ｒ^２は二価以上の有機基であり、ｎは２以上の整数である。）

(In the above formula, R ¹ is a group selected from Ph, CN, CO ₂ R ³ (R ³ is a monovalent organic group), R ² is a divalent or higher organic group, and n is It is an integer of 2 or more.)

（上の式中、Ｒ^４はＨ、Ｍｅ、炭素数１から２０の有機基から選ばれる基であり、且つ、Ｒ^５は二置換以上のベンゼン基、ナフタレン基であり、ｎは２以上の整数である。）

(In the above formula, R ⁴ is a group selected from H, Me, and an organic group having 1 to 20 carbon atoms, and R ⁵ is a benzene group or a naphthalene group having two or more substitutions, and n is two or more. (It is an integer.)

（上の式中、Ｒ^６はＨ、Ｍｅ、ＣＮ、炭素数１から２０の有機基から選ばれる基であり、且つ、Ｒ^７は二価以上の有機基であり、ｎは２以上の整数である。）これらの中でも、ジビニルベンゼンあるいはジイソプロペニルベンゼンが好ましい。

(In the above formula, R ⁶ is a group selected from H, Me, CN, an organic group having 1 to 20 carbon atoms, R ⁷ is a divalent or higher organic group, and n is an integer of 2 or higher. Among these, divinylbenzene or diisopropenylbenzene is preferable.

The vinyl monomer of the present invention is not particularly limited, but is preferably a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl monomer.

According to the present invention, in a method for obtaining a polymer having a star structure in which the structure is easily controlled from various radical polymerizable monomers, the reaction can be controlled better than the conventional methods.

The present invention relates to a transition metal catalyst (b) in a process for producing a polymer in which a compound (a) having two or more polymerizable carbon-carbon double bonds is added near the end point of atom transfer radical polymerization of a vinyl monomer. ) Is used in a total amount of 0.5 molar equivalent or more with respect to the initiator, and relates to a method for producing a star-shaped vinyl polymer.
<Monomer>
It does not specifically limit as a monomer used for superposition | polymerization of this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used singly or a plurality thereof may be copolymerized. When copolymerizing, random copolymerization or block copolymerization may be used, but block copolymerization is preferred. Of these, a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl monomer are preferred from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
<Atom transfer radical polymerization>
The atom transfer radical polymerization used in the present invention will be described below.

Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition in the present invention is also the latter. In recent years, living radical polymerization has been actively researched by various groups. Examples include cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 116, 7943), those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), organic halides, etc. And atom transfer radical polymerization using a transition metal complex as a catalyst. In atom transfer radical polymerization, polymerization is performed using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. Specifically, Matyjazewski et al. Am. Chem. Soc. 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866; or Sawamoto et al., Macromolecules 1995, 28, 1721, International Publications WO96 / 30421 and WO97 / 18247. According to these methods, in general, the polymerization rate is very high, and the radical polymerization is likely to cause a termination reaction such as coupling between radicals, but the polymerization proceeds in a living manner and the molecular weight distribution is narrow (that is, Mw / Mn). A polymer having a value of about 1.1 to 1.5 is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a halogen It is preferable to use a sulfonylated compound as an initiator. The transition metal compound used as a catalyst for the living radical polymerization is not particularly limited, and is preferably a transition metal compound of a group 7, 8, 9, 10, 11 or more preferably a transition metal compound. Examples of the compound include zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Among these, a copper compound is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

In the atom transfer radical polymerization, although not limited, an organic halide (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position) or a sulfonyl halide is used as an initiator. For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2,
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
^{_{R 8 -C (H) (X}} ) -CO 2 R 9, R 8 -C (CH 3) (X) -CO 2 R 9, R 8 -C (H) (X) -C (O) R 9 _{^{, R 8 -C (CH 3)}} (X) -C (O) R 9,
(Wherein R ⁸ and R ⁹ are the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and X is chlorine. , Bromine, or iodine)
^{_{R 8 -C 6 H 4 -SO 2}} X,
(In the above formulas, R ⁸ hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or iodine)
Etc.

In atom transfer radical polymerization, an initiator having two or more initiation sites is often used. In the present invention, a monofunctional initiator is preferred.

As an initiator of atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at the end of the main chain is produced, and a polymer having a functional group at the end is obtained by coupling it with the method of the present invention. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like. When an initiator having a crosslinkable silyl group is used, a star polymer having a crosslinkable silyl group at the end of the present invention can be easily obtained. In addition, there is a method in which an initiator having another functional group is used to produce a star polymer having these functional groups at its terminal, and then converted to a crosslinkable silyl group by a method described later.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula 6.
^{R 11 R 12 C (X)} -R 13 -R 14 -C (R 10) = CH 2 (6)
(Wherein R ¹⁰ is hydrogen or a methyl group, R ¹¹ and R ¹² are hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or aralkyl, or those interconnected at the other end. , R ¹³ represents —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ¹⁴ represents a direct bond, or 1 carbon atom. -20 divalent organic groups which may contain one or more ether linkages, X is chlorine, bromine or iodine)
Specific examples of the substituents R ¹¹ and R ¹² include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R ¹¹ and R ¹² may be linked at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula 6 include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n CH = CH 2, (H 3 C) 2 C (X _{) C (O) O (CH} 2) n CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O (CH 2) n CH = CH 2,

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、

(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m CH = _{CH 2, (H 3 C)} 2 C (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2, CH 3 CH 2 C (H) (X) C (O) O _{(CH 2) n O (CH} 2) m CH = CH 2,

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
アルケニル基を有する有機ハロゲン化物としてはさらに一般式７で示される化合物が挙げられる。
Ｈ_２Ｃ＝Ｃ（Ｒ^１０）−Ｒ^１４−Ｃ（Ｒ^１１）（Ｘ）−Ｒ^１５−Ｒ^１２ （７）

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) _{n -CH = CH 2, o,} m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) -C _{6 H 4 - (CH 2)} n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) _{n -O- (CH 2) m CH} = CH 2,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2, o, m, p-CH 3 C (H) (X) -C 6 H 4 -O- _{(CH 2) n -CH = CH} 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 C (H) (X) _{-C 6 H 4 -O- (CH 2} ) n -O- (CH 2) m -CH = CH 2, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - O— (CH ₂ ) _n —O— (CH ₂ ) _m —CH═CH ₂ ,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
The organic halide having an alkenyl group further includes a compound represented by the general formula 7.
^{_{H 2 C = C (R 10}} ) -R 14 -C (R 11) (X) -R 15 -R 12 (7)

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ and X are the same as above, R ¹⁵ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) Or an o-, m-, p-phenylene group)
R ¹⁴ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (may contain one or more ether bonds), and in the case of a direct bond, carbon to which a halogen is bonded Is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group or a phenylene group as R ¹⁵ , and a direct bond may be used. When R ¹⁴ is not a direct bond, R ¹⁵ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

To specifically illustrate the compound of formula 7,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X, CH 2 = CHC (H) (X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3, _{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5, CH 2 = CHC (H) (X) CH (CH 3) 2, CH 2 = CHC ( _{H) (X) C 6 H} 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5, CH 2 = CHCH 2 C (H) (X) -CO 2 R, CH 2 = CH (CH _{2) 2 C (H) (} X) -CO 2 R, CH 2 = CH (CH 2) 3 C (H) (X) -CO 2 R, CH 2 = CH (CH 2) 8 C (H) ( _{X) -CO 2 R, CH 2} = CHCH 2 C (H) (X) -C 6 H 5, CH 2 = CH (CH 2) 2 C (H) (X) -C 6 _{H 5, CH 2 = CH (} CH 2) 3 C (H) (X) -C 6 H 5,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X, o-, m-, p-CH 2 = CH- (CH 2) n -O-C ₆ H ₄ -SO ₂ X,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula 8.
^{R 11 R 12 C (X)} -R 13 -R 14 -C (H) (R 10) CH 2 - [Si (R 16) 2-b (Y) b O] m -Si (R 17) 3- _a (Y) _a (8)
(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and X are the same as above, R ¹⁶ and R ¹⁷ are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and when two or more R ¹⁶ or R ¹⁷ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and Y represents two or more When present, they may be the same or different, a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer from 0 to 19. (Provided that a + mb ≧ 1)
If the compound of the general formula 8 is specifically exemplified,
_{XCH 2 C (O) O (} CH 2) n Si (OCH 3) 3, CH 3 C (H) (X) C (O) O (CH 2) n Si (OCH 3) 3, (CH 3) 2 _{C (X) C (O)} O (CH 2) n Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n Si (CH 3) (OCH 3) 2, CH 3 C (H) _{(X) C (O) O} (CH 2) n Si (CH 3) (OCH 3) 2, (CH 3) 2 C (X) C (O) O (CH 2) n Si (CH 3) (OCH ₃ ) ₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3, H 3 CC (H) (X) C (O) O (CH 2) n O (CH 2) m Si (OCH ₃ ) ₃ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m Si (OCH ₃ ) ₃ , CH ₃ CH ₂ C (H) (X _{) C (O) O (CH} 2) n O (CH 2) m Si (OCH 3) 3, XCH 2 C (O) O (CH 2) n O (CH 2) m Si (CH 3) (OCH 3 ) ₂ , H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m —Si (CH ₃ ) (OCH ₃ ) ₂ , (H ₃ C) ₂ C (X) _{C (O) O (CH 2} ) n O (CH 2) m -Si (CH 3) (OCH 3) 2, CH 3 CH 2 C (H) (X) C (O) O (CH _{2) n O (CH 2)} m -Si (CH 3) (OCH 3) 2,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2 _{) 2 Si (OCH 3) 3} , o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3, o, m, p- _{XCH 2 -C 6 H 4 - (} CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3 _{) 3, o, m, p} -CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3, o, m, p-XCH 2 -C 6 H _{4 - (CH 2) 2 -O-} (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 H 4 - (CH 2) 2 -O − _{CH 2) 3 Si (OCH 3} ) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH _{3) 3, o, m,} p-XCH 2 -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 C (H) (X) -C 6 _{H 4 -O- (CH 2) 3} Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si ( _{OCH 3) 3, o, m} , p-XCH 2 -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3, o, m, p-CH 3 _{C (H) (X) -C} 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3, o, m, p-CH 3 CH 2 C (H) ( X) _{C 6 H 4 -O- (CH 2} ) 2 -O- (CH 2) 3 Si (OCH 3) 3,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.

Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula 9.
_{^{(R 17) 3-a (}} Y) a Si- [OSi (R 16) 2-b (Y) b] m -CH 2 -C (H) (R 10) -R 14 -C (R 11) ( X) -R ¹⁵ -R ¹² (9)
(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , a, b, m, X, Y are the same as above)
If such a compound is specifically illustrated,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5, (CH 3 O) 2 (CH 3) SiCH 2 CH 2 C (H) (X) C 6 H 5, (CH _{3 O) 3 Si (CH 2} ) 2 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 2 C (H) (X) -CO 2 R, _{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H) (X) -CO 2 _{R, (CH 3 O) 3} Si (CH 2) 4 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 4 C (H) (X) - _{CO 2 R, (CH 3 O} ) 3 Si (CH 2) 9 C (H) (X) -CO 2 R, (CH 3 O) 2 (CH 3) Si (CH 2) 9 C (H) (X _{) -CO 2 R, (CH 3} O) 3 Si (CH 2) 3 C (H) (X) -C 6 H 5, (CH 3 O) 2 (CH 3) Si (CH 2) 3 C (H _{) (X) -C 6 H 5} , (CH 3 O) 3 Si (CH 2) 4 C (H) (X) -C 6 H 5, (CH 3 O) 2 (CH 3) Si (CH 2) ₄ C (H) (X) -C ₆ H ₅ ,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
本発明のリビングラジカル重合は無溶剤または各種の溶剤中で行うことができる。上記溶媒としては、例えば、ベンゼン、トルエン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン、ジフェニルエーテル、アニソール、ジメトキシベンゼン等のエーテル系溶媒；塩化メチレン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒等が挙げられる。これらは、単独又は２種以上を混合して用いることができる。また、エマルジョン系もしくは超臨界流体ＣＯ_２を媒体とする系においても重合を行うことができる。

(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The living radical polymerization of the present invention can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; acetone Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; acetic acid Examples thereof include ester solvents such as ethyl and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used individually or in mixture of 2 or more types. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

The polymerization of the present invention is not particularly limited, but can be carried out in the range of 0 ° C to 200 ° C, preferably room temperature to 150 ° C.
<Synthesis of star polymer>
When a compound (a) having two or more polymerizable carbon-carbon double bonds is added in the vicinity of the end point of such atom transfer radical polymerization, a coupling reaction occurs to produce a polymer having a star structure. . The vicinity of the end point of the polymerization is preferably when 80% or more of the monomer has reacted, more preferably 90% or more, particularly preferably 95% or more, most preferably 99% or more. It is the time of reaction.

The compound (a) having two or more polymerizable carbon-carbon double bonds is not limited, but is selected from compounds represented by the general formulas 1, 2, and 3.

（上の式中、Ｒ^１はＰｈ、ＣＮ、ＣＯ_２Ｒ^３（Ｒ^３は一価の有機基）から選ばれる基であり、且つ、Ｒ^２は二価以上の有機基であり、ｎは２以上の整数である。）

(In the above formula, R ¹ is a group selected from Ph, CN, CO ₂ R ³ (R ³ is a monovalent organic group), R ² is a divalent or higher organic group, and n is It is an integer of 2 or more.)

（上の式中、Ｒ^４はＨ、Ｍｅ、炭素数１から２０の有機基から選ばれる基であり、且つ、Ｒ^５は二置換以上のベンゼン基、ナフタレン基であり、ｎは２以上の整数である。）

(In the above formula, R ⁴ is a group selected H, Me, organic group having 1 to 20 carbon atoms, and, R ⁵ is di-substituted or more benzene group, a naphthalene radical, n is 2 or more (It is an integer.)

（上の式中、Ｒ^６はＨ、Ｍｅ、ＣＮ、炭素数１から２０の有機基から選ばれる基であり、且つ、Ｒ^７は二価以上の有機基であり、ｎは２以上の整数である。）
上記各式において、Ｒ^３、Ｒ^４及びＲ^６で表される一価の有機基としては、特に限定されないが、以下のものが例示される。
−（ＣＨ_２）_ｎ−ＣＨ_３、−ＣＨ（ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、−ＣＨ（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、−ＣＨ（ＣＨ_２ＣＨ_３）_２、−Ｃ（ＣＨ_３）_２−（ＣＨ_２）_ｎ−ＣＨ_３、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、−Ｃ_６Ｈ_５、−Ｃ_６Ｈ_５（ＣＨ_３）、−Ｃ_６Ｈ_５（ＣＨ_３）_２、−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_５、−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_５（ＣＨ_３）、−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_５（ＣＨ_３）_２
（ｎは０以上の整数で、各基の合計炭素数は２０以下）
上記各式において、Ｒ^２及びＲ^７は、二価以上の有機基であり、限定はされないが、以下のようなものが例示される。
−（ＣＨ_２）_ｎ −（ｎは、１〜２０の整数を表す。）；−ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_２ＣＨ_３）_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−；−（ＣＨ_２）_ｎ−Ｏ−ＣＨ_２−（ｎは、１〜１９の整数を表す。）；−ＣＨ（ＣＨ_３）−Ｏ−ＣＨ_２−、−ＣＨ（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_２ＣＨ_３）_２−Ｏ−ＣＨ_２−、−（ＣＨ_２）_２−ＯＣ（Ｏ）−；−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）−（ＣＨ_２）_ｍ−（ｍ及びｎは、同一又は異なって、０〜１９の整数を表す。ただし、０≦ｍ＋ｎ≦１９を満たす。）；−（ＣＨ_２）_ｎ−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−（ｍ及びｎは、同一又は異なって、０〜１９の整数を表す。ただし、０≦ｍ＋ｎ≦１９を満たす。）；−ＣＨ_２−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_２−Ｏ−ＣＨ_２−、−ＣＨ（ＣＨ_３）−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_２−Ｏ−ＣＨ_２−、等が挙げられる。

(In the above formula, R ⁶ is a group selected from H, Me, CN, an organic group having 1 to 20 carbon atoms, R ⁷ is a divalent or higher organic group, and n is an integer of 2 or higher. .)
In each of the above formulas, the monovalent organic group represented by R ³ , R ⁴ and R ⁶ is not particularly limited, but examples thereof include the following.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 5 (CH 3)} , - C 6 H 5 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 5 (CH 3), - ( _{CH 2) n -C 6 H 5} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
In the above formulas, R ² and R ⁷ are divalent or higher organic groups and are not limited, but the following are exemplified.
_{- (CH 2) n - (} n represents an integer of _{1~20.); - CH (CH} 3) -, - CH (CH 2 CH 3) -, - C (CH 3) 2 -, - C _{(CH 3) (CH 2 CH} 3) -, - C (CH 2 CH 3) 2 -, - CH 2 CH (CH 3) - ;-( CH 2) n -O-CH 2 - (n is 1 represents an integer of _{~19); -. CH (CH} 3) -O-CH 2 -, - CH (CH 2 CH 3) -O-CH 2 -, - C (CH 3) 2 -O-CH 2 - _{, -C (CH 3) (CH} 2 CH 3) -O-CH 2 -, - C (CH 2 CH 3) 2 -O-CH 2 -, - (CH 2) 2 -OC (O) -; - _{(CH 2) n -OC (O} ) - (CH 2) m - (m and n are the same or different and each represents an integer of 0 to 19 provided that satisfy 0 ≦ m + n ≦ 19. .) _{- (CH 2) n -C (} O) O- (CH 2) m -; (m and n are the same or different and each represents an integer of 0 to 19 provided that satisfy 0 ≦ m + n ≦ 19. .) _{-CH 2 -C (O) O- (} CH 2) 2 -O-CH 2 -, - CH (CH 3) -C (O) O- (CH 2) 2 -O-CH 2 -, include etc It is done.

R ² and R ⁷ may contain a benzene ring. Examples of this _{case, o-, m-, p-C} 6 H 4 -, o-, m-, p-C 6 H 4 -CH 2 -, o-, m-, p-C 6 H _{4 -O-CH 2 -, o-} , m-, p-C 6 H 4 -O-CH (CH 3) -, o-, m-, p-C 6 H 4 -O-C (CH 3) _{2 -; o-, m-, p} -C 6 H 4 - (CH 2) n - (. n is an integer of _{0~14); o-, m-, p} -C 6 H 4 -O - _(CH 2) n- _(n represents an integer of _{0~14.); o-, m-,} p-CH 2 -C 6 H 4 -, o-, m-, p-CH 2 -C _{6 H 4 -CH 2 -, o-} , m-, p-CH 2 -C 6 H 4 -O-CH 2 -, o-, m-, p-CH 2 -C 6 H 4 -O-CH ( _{CH 3) -; o-, m-} , p-CH 2 -C 6 H 4 -O-C (CH 3) _{2 -; o-, m-, p} -CH 2 -C 6 H 4 - (CH 2) n - (. N is an integer of 0~13); o-, m-, p -CH 2 - _{C 6 H 4 -O- (CH 2} ) n - (. n is an integer of 0~13); o-, m-, p -C (O) -C 6 H 4 -C (O) O _{- (CH 2) n - (} n represents an integer of 0 to 12.), and the like.

If the said compound is illustrated concretely, it will not specifically limit, but 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, , 4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4, Examples include polyvinyl aromatic compounds such as 5,8-tributylnaphthalene and 2,2′-divinyl-4-ethyl-4′-propylbiphenyl, and poly (meth) acrylates such as ethylene glycol dimethacrylate and ethylene glycol diacrylate. . Of these, polyvinyl aromatic compounds are preferable, and divinylbenzene is more preferable.

The amount of the compound having two or more polymerizable alkenyl groups to be added is not particularly limited, but preferably the number of olefins is equal to or more than the number of growing terminals of the polymer as an arm. When the amount is small, a large amount of uncoupled polymer may remain. More preferably, the amount of the compound having two or more polymerizable alkenyl groups to be added is not particularly limited, but the number of olefins is more preferably 20 times or less the number of growing terminals of the polymer as an arm. Is 10 times or less, particularly preferably 5 times or less.

The reaction conditions after the addition of the coupling agent are not particularly limited, but may be the same as the polymerization conditions of the polymer serving as the arm.
<Catalyst amount>
The present invention relates to a transition metal catalyst (b) in a process for producing a polymer in which a compound (a) having two or more polymerizable carbon-carbon double bonds is added near the end point of atom transfer radical polymerization of a vinyl monomer. ) Is used in a total amount of 0.5 molar equivalents or more, more preferably 0.7 equivalents or more, and more preferably 1 molar equivalents or more with respect to the initiator.

In the process for producing a polymer in which the inventors perform atom transfer radical polymerization of a vinyl-based monomer and then add a compound (i) having two or more polymerizable carbon-carbon double bonds in the vicinity of the polymerization end point. Found that the amount of catalyst was important.

In atom transfer radical polymerization, the polymerization reaction proceeds even when the amount of the transition metal compound (c) is less than the growth terminal (so-called catalytic amount). That is, the polymerization can be controlled even with a smaller amount of catalyst than the growth terminal. However, when the radicals at the growing ends are coupled to each other, the metal of the transition metal compound (C) has a higher oxidation number by the amount of the coupling, and the polymerization reaction is slowed down. In ordinary atom transfer radical polymerization systems, radical-radical coupling reactions do not occur so much, so this is not a problem. However, in the production of the star polymer of the present invention, the growing ends are bundled together so that they are close to each other. A ring reaction is likely to occur. Therefore, it is considered that a catalyst amount is required to some extent or more with respect to the growth end.

As the transition metal catalyst (b) and / or the transition metal compound (c) and / or the additional catalyst (d) used in the present invention, those already disclosed in the description of the atom transfer radical polymerization may be preferably used. it can.

On the other hand, when the amount of the transition metal compound (c) is increased, the polymerization rate tends to increase, the heat generation becomes large, and the control of the polymerization tends to be difficult. In order to solve this problem and to achieve the object of the present invention, after adding a compound (i) having two or more polymerizable carbon-carbon double bonds, an additional catalyst (d) is used as zero valence. It is preferable to add copper, a transition metal compound, or a transition metal complex. The additional catalyst (d) may be the same compound as the transition metal compound (c) used for the polymerization of the vinyl monomer until now, but it is more preferable that the oxidation number of the metal is smaller.

The transition metal compound (c) and / or the transition metal of the additional catalyst (d) is not particularly limited, but copper, nickel, ruthenium and iron are preferable, and copper is particularly preferable.

The additional catalyst (d) is more preferably zero-valent copper or a complex of zero-valent copper.

In the present invention, zero-valent copper, a transition metal compound, or the transition metal complex itself may be added as an additional catalyst (d), and a compound that is a ligand of the transition metal compound (c) (e.g. ) May be added (this is the method invented by the present inventors). This is because a necessary amount of transition metal compound (C) is added to the polymerization system from the beginning, and a ligand capable of forming a complex with the metal and generating catalytic activity is added later as needed. Is the method. The compound (e) serving as a ligand for the transition metal compound (c) is not particularly limited, but an amine-based ligand such as hexamethyldiethylenetriamine is preferable. Specifically, for example, by adding hexamethyldiethylenetriamine to CuBr previously added to the polymerization system, the catalytic activity corresponding to the added amount of this triamine can be expressed.

Examples of the compound (e) as a ligand of the transition metal compound (c) include 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexa Polyamines such as methyltris (2-aminoethyl) amine are preferred.
<Product>
The star polymer produced by the method of the present invention is not limited, but the molecular weight distribution, that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Another feature is that (Mw / Mn) is narrow. The value of the molecular weight distribution is preferably 3 or less, more preferably 2 or less, more preferably 1.8 or less, particularly preferably 1.6 or less, particularly preferably 1.4 or less. Yes, most preferably 1.3 or less. The GPC measurement in the present invention is not particularly limited, but usually, chloroform is used as the mobile phase, and the measurement is performed with a polystyrene gel column. The number average molecular weight and the like can be determined in terms of polystyrene. It is known that the molecular weight measured by GPC of a star polymer is generally lower than the true molecular weight.
<Application>
The polymer produced in the present invention is not limited, but can be used in a lubricating oil composition or the like. In the case of a polymer having a functional group at the terminal, the functional group such as hydroxyl group, crosslinkable silyl group, or alkenyl group is used as it is or converted to another functional group such as crosslinkable silyl group. An elastomer can be formed by causing a crosslinking reaction. For example, sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electrical and electronic use, films, gaskets, various molding materials, artificial marble, etc. is there.

Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.

Example 1
In a 100 mL glass reaction vessel, methyl 2-bromopropionate (0.97 mL, 1.46 g, 8.72 mmol) was used as an initiator, and cuprous bromide (1.00 g, 6.98 mmol) was added to a transition metal compound (HA). ), Butyl acrylate (50.0 mL, 44.7 g, 0.35 mol) was polymerized at 70 ° C. in the presence of acetonitrile (5 mL) using pentamethyldiethylenetriamine (0.12 mL, 0.56 mmol) as a ligand. . After 90 minutes, when the polymerization rate was 98%, divinylbenzene (1.86 mL, 13.1 mmol) was added, and successive sampling was performed while continuing the polymerization. After 390 minutes, pentamethyldiethylenetriamine (0.40 mL, 1.92 mmol) was added, and sampling was performed after 540 minutes. Further, pentamethyldiethylenetriamine (0.80 mL, 3.83 mmol) was added, and the reaction was stopped after 720 minutes. FIG. 1 shows the change over time of the GPC analysis of the sample from the polymerization system. The linear polymer before addition of divinylbenzene has a number average molecular weight Mn = 6000 and a molecular weight distribution Mw / Mn = 1.38, and the addition of divinylbenzene does not show much increase in molecular weight, and Mn even after 390 minutes. = 6200 and monodisperse. After addition of pentamethyldiethylenetriamine, the formation of a star polymer was confirmed, and after 540 minutes it became bimodal with Mn = 11000, and finally it became unimodal with a number average molecular weight of 33,000 and a molecular weight distribution of 1.6. It was. It can be seen that almost all linear polymers become star polymers, and the resulting star polymers are monodispersed and have a very narrow molecular weight distribution. From this result, the amount of the catalyst is important for the synthesis of the controlled star polymer, and it is preferable to add the compound (e) after the addition of divinylbenzene in consideration of the control of the polymerization of the arm part. it is obvious.

FIG. 2 is a GPC chart (change with time) of a star polymer obtained by the method of Example 1. FIG.

Claims (10)

In the process of producing a polymer in which a compound (a) having two or more polymerizable carbon-carbon double bonds is added near the end point of atom transfer radical polymerization of a vinyl monomer, a transition metal catalyst (b) is started. A method for producing a star-shaped vinyl polymer characterized by using a total of 0.5 molar equivalents or more based on the agent,
In the vicinity of the polymerization end point of the atom transfer radical polymerization of the vinyl monomer using the transition metal compound (c), after adding the compound (a) having two or more polymerizable carbon-carbon double bonds, an additional catalyst ( (D) A method for producing a star-shaped vinyl polymer characterized by adding metallic copper or a transition metal compound. The method for producing a star-shaped vinyl polymer according to claim 1, wherein the additional catalyst (d) is a transition metal complex. The method for producing a star-shaped vinyl polymer according to claim 1 or 2, wherein the transition metal catalyst (b) is used in a total of 1 molar equivalent or more with respect to the initiator. 4. The star-shaped vinyl polymer according to claim 1, wherein the oxidation number of the metal of the additional catalyst (d) is smaller than that of the metal of the transition metal compound (c). 5. Production method. The transition metal compound (c) and / or the transition metal of the additional catalyst (d) is at least one metal selected from the group consisting of copper, nickel, ruthenium and iron. The manufacturing method of the star-shaped vinyl polymer as described in any one of -4. 6. The method for producing a star-shaped vinyl polymer according to claim 5, wherein the transition metal compound (c) and / or the transition metal of the additional catalyst (d) is copper. The method for producing a star-shaped vinyl polymer according to claim 4, wherein the additional catalyst (d) is metallic copper or a complex of zero-valent copper. 8. The compound (a) having two or more polymerizable carbon-carbon double bonds is represented by a chemical formula selected from the group consisting of the general formulas 1, 2, and 3. A method for producing a star-shaped vinyl polymer according to claim 1.

(In the above formula, R ¹ is a group selected from Ph, CN, CO ₂ R ³ (R ³ is a monovalent organic group), R ² is a divalent or higher organic group, and n is It is an integer of 2 or more.)

(In the above formula, R ⁴ is a group selected from H and an organic group having 1 to 20 carbon atoms, and R ⁵ is a disubstituted or higher benzene group or naphthalene group, and n is an integer of 2 or more. is there.)

(In the above formula, R ⁶ is a group selected from H, CN, and an organic group having 1 to 20 carbon atoms, R ⁷ is a divalent or higher organic group, and n is an integer of 2 or higher. .)
However, in the general formula 1, 2 and 3, an organic group of the monovalent organic group in ^{R 3,} carbon atoms of 1 for ^{R 4} and ^{R 6} 20 _{is, - (CH 2) n -CH} 3, -CH (CH _{3) - (CH 2) n} -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) 2, -C (CH 3) 2 - (CH _{2) n -CH 3, -C (} CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, -C 6 H 4 (CH 3), - C 6 H 3 (CH ₃ ) ₂ , — (CH ₂ ) _n —C ₆ H ₅ , — (CH ₂ ) _n —C ₆ H ₄ (CH ₃ ), or — (CH ₂ ) _n —C ₆ H ₃ (CH ₃ ) ₂ (n is an integer of 0 or more and the total carbon number of each group is 20 or less)), and the divalent or higher organic group in R ² and R ⁷ is — (CH ₂ ) _n — ( n represents an integer of 1 to 20 _{.), - CH (CH 3} ) -, - CH (CH 2 CH 3) -, - C (CH 3) 2 -, - C (CH 3) (CH 2 CH 3) -, - C (CH 2 CH ₃ ) ₂ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) _n —O—CH ₂ — (n represents an integer of 1 to 19), —CH (CH ₃ ) —O—. _{CH 2 -, - CH (CH} 2 CH 3) -O-CH 2 -, - C (CH 3) 2 -O-CH 2 -, - C (CH 3) (CH 2 CH 3) -O-CH 2 _{-, - C (CH 2 CH} 3) 2 -O-CH 2 -, - (CH 2) 2 -OC (O) -, - (CH 2) n -OC (O) - (CH 2) m - ( m and n are the same or different and each represents an integer of 0 to 19. However, 0 ≦ m + n ≦ 19 is satisfied.), — (CH ₂ ) _n —C (O) O— (CH ₂ ) _m — ( m and n are the same or different and represent an integer of 0 to 19. Satisfies 0 ≦ m + n ≦ 19) , -. CH 2 -C (O) O- (CH 2) 2 -O-CH 2 -, - CH (CH 3) -C (O) O- (CH 2) _{2 -O-CH 2 -, o-} , m-, p-C 6 H 4 -, o-, m-, p-C 6 H 4 -CH 2 -, o-, m-, p-C 6 H _{4 -O-CH 2 -, o-} , m-, p-C 6 H 4 -O-CH (CH 3) -, o-, m-, p-C 6 H 4 -O-C (CH 3) _{2 -, o-, m-, p} -C 6 H 4 - (CH 2) n - (n represents an integer of 0 to 14. ), O-, m-, p- C 6 H 4 -O- (CH 2) n- (n represents an integer of 0~14.), O-, m-, p-CH 2 -C 6 _{H 4 -, o-, m-,} p-CH 2 -C 6 H 4 -CH 2 -, o-, m-, p-CH 2 -C 6 H 4 -O-CH 2 -, o-, m _{-, p-CH 2 -C 6} H 4 -O-CH (CH 3) -; o-, m-, p-CH 2 -C 6 H 4 -O-C (CH 3) 2 -, o-, _{m-, p-CH 2 -C 6} H 4 - (CH 2) n - (. n is an integer of 0~13), o-, m-, p -CH 2 -C 6 H 4 -O _{- (CH 2) n - (} . n represents an integer of 0 to 13), or o-, m-, p-C ( O) -C 6 H 4 -C (O) O- (CH 2) _n— (n represents an integer of 0 to 12). 9. The method for producing a star-shaped vinyl polymer according to claim 8, wherein the compound (a) having two or more polymerizable carbon-carbon double bonds is divinylbenzene or diisopropenylbenzene. The vinyl monomer is at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. 9. A process for producing the star-shaped vinyl polymer according to 9.

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