JP2013144786A - Chain transfer agent having condensed polycyclic aromatic skeleton, and polymer having the condensed polycyclic aromatic skeleton and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new type of a chain transfer agent which does not have problems associated with odor, corrosivity and hygroscopicity, is environment-friendly, and has high chain transfer ability, and further to provide a polymer using the chain transfer agent, which has a functional group at the end and is imparted with a condensed polycyclic aromatic skeleton, and its production method.SOLUTION: This chain transfer agent includes a condensed polycyclic aromatic skeleton expressed by general formula (1) (wherein, n=1-4; R's are each independently hydrogen, an alkyl, aryl, aralkyl, hydroxy, alkoxy, aryloxy group or a halogen atom; X and Y are each independently a hydrogen atom, a hydroxy, alkyl, amino group, a halogen atom or six-membered rings bonded with each other).

Description

The present invention relates to a chain transfer agent useful for obtaining a low molecular weight polymer and for obtaining a polymer having a condensed polycyclic aromatic skeleton in the molecule. In particular, the present invention relates to a chain transfer agent having a condensed polycyclic aromatic skeleton applicable to a radical polymerizable compound, a polymer produced using the same, and a method for producing the polymer.

Radical polymerizable compounds are organic compounds that are widely used industrially as raw materials for synthetic resins. Examples of such radical polymerizable compounds include acrylic acid, methacrylic acid, esters thereof, and styrene compounds. A wide variety of compounds are known.

In the polymerization process of these radically polymerizable compounds, it is beneficial to adjust the molecular weight of the produced polymer according to the intended use. In particular, when used for applications such as coating agents, adhesives, pressure-sensitive adhesives, paper strength enhancers, binders, resists, etc., molecular weight adjustment is an important technique.

There are various techniques for adjusting the molecular weight in the polymerization reaction of the radical polymerizable compound, but a method of adding a chain transfer agent to the polymerization system is often used. As the chain transfer agent, conventionally, halogenated hydrocarbons typified by carbon tetrachloride, alkyl mercaptan compounds typified by t- or n-dodecyl mercaptan, or sulfide compounds have been used (for example, patent documents). 1-3.)

For example, low molecular weight acrylic polymers have been widely used for applications such as paints, adhesives, and sealing materials. When producing such low molecular weight acrylic polymers, mercaptans as chain transfer agents are used. A compound is used (for example, refer patent documents 4-6).

In the polymerization of styrene, mercaptan chain transfer agents are added to adjust the average molecular weight, molecular weight distribution, melt flow index, and the like (see, for example, Patent Documents 7 and 8).

Also, in the production of polymerized toners used in copiers and printers, t-dodecyl mercaptan, 2-mercaptoethanol, etc. are used to obtain a low molecular weight and sharp molecular weight distribution when polymerizing styrene monomers and acrylic monomers. Mercaptan-based or halogen-based chain transfer agents such as carbon tetrachloride and trichlorobromomethane are used (see, for example, Patent Documents 9, 10, and 11).

Furthermore, since the resist for flat printing and the resist for the printed circuit board require water resistance and film strength of a portion cured by exposure, it is necessary to adjust the polymerization state with a chain transfer agent (see Patent Document 12). ).

On the other hand, chain transfer agents are known not only to adjust the molecular weight as described above, but also to impart their own residues to the polymer ends from the reaction mechanism (see, for example, Non-Patent Documents 1 to 3). .) Utilizing this fact, a technique for imparting a functional group to a polymer terminal by using a chain transfer agent having a functional group has also been proposed (see, for example, Patent Documents 13 and 14, Non-Patent Documents 4 and 5). .)

On the other hand, the compound having a condensed polycyclic aromatic skeleton of the present invention has a quinone skeleton. There are several examples where such a compound having a quinone skeleton is used as a polymerization inhibitor. For example, an example in which benzoquinone is used as a polymerization inhibitor is known (see Patent Document 15). However, this benzoquinone is used as a polymerization inhibitor and is not used as a chain transfer agent. Moreover, there is no suggestion about the effect as a chain transfer agent. Further, as a result of studies on the benzoquinone by the present inventors, it has been found that the present invention does not have sufficient performance as a chain transfer agent as shown in Comparative Examples.

JP 2009-522411 A JP 2008-519137 A JP-A-9-118841 Japanese Patent Publication No.58-455 Japanese Patent Laid-Open No. 55-5950 Japanese Examined Patent Publication No. 46-40693 JP 2002-241413 A JP 2009-197105 A JP-A-7-330912 JP 2004-224840 A JP 2010-197954 A JP 2006-91479 A Japanese Patent Publication No.57-10850 JP 2010-222285 A Special table 2001-514280 gazette

By G. Odian, Principles of Polymerization, 4th edition, 2004, John Wiley & Sons, New York, 238 pages Takatsu Otsu, “Chemistry of Polymer Synthesis” (Chemical Doujin, 1979) p. Edited by Mikiharu Konoike, “Radical Polymerization Handbook” (NTS, 2010), p. 47 Tanaka Seifumi, Nishida Haruo, Endo Go, Macromolecules, 2009, 42, 293-298 Tetsuo Ogawa, paint research (Kansai Paint), No. 137, Oct, 2001, 11 pages.

Conventionally used chain transfer agents such as halogenated hydrocarbons, especially carbon tetrachloride, have environmental problems such as destroying the earth's ozone layer, and alkyl mercaptans and sulfides have strong odors and handling problems. In addition, there is a problem that odor remains in the resin. In addition, these thiol-based chain transfer agents also have a problem that storage stability is inferior because viscosity increase or gelation of the curable composition occurs because an ene-thiol reaction occurs during storage. Furthermore, these thiol chain transfer agents also have a problem of generating a sulfur-containing gas and desorbing from the polymer to corrode the metal.

In addition, when these chain transfer agents are used, naturally, sulfur or the like is taken into the polymerization terminal, corrodes the container or the like, the resin becomes hygroscopic, and becomes an environmental problem when the resin is disposed of. On the other hand, alpha methyl styrene dimer has few environmental problems and is widely used, but still has a problem of having an odor.

In addition, it is known that a chain transfer agent is added to the end of a growing polymer to cause chain transfer, and it has been proposed to produce a polymer having a functional group at the end using this (for example, Patent Document 11). 12, see Non-Patent Documents 4 and 5.). However, all of these chain transfer agents are derivatives of the above-mentioned halogenated hydrocarbons, alkyl mercaptans, and alphamethylstyrene dimers, and it must be said that they have the above-mentioned drawbacks as they are.

Therefore, an object of the present invention is to provide a new type of chain transfer agent which is free from problems of odor, corrosivity and hygroscopicity, is environmentally friendly and has a high chain transfer ability. Furthermore, the objective of this invention is providing the polymer provided with the condensed polycyclic aromatic skeleton which has a functional group at the terminal, and its manufacturing method.

Therefore, in order to solve the above problems, the present inventors have intensively studied a chain transfer agent of a radical polymerizable compound, and as a result, a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention has been conventionally known. In spite of having a completely different structure from the chain transfer agent, the polymer has an excellent chain transfer effect and can produce a polymer having a condensed polycyclic aromatic skeleton derived from the chain transfer agent of the present invention in the molecule. The present invention has been completed.

That is, the first invention in the present invention resides in a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (1).

(In the formula (1), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent, and are saturated or unsaturated 6-membered The 6-membered ring formed by X and Y may be further substituted with an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom. )

  According to a second invention, in the general formula (1), n is 4, R is a hydrogen atom, X and Y are hydrogen atoms, the condensed polycycle according to the first invention It exists in the chain transfer agent which has an aromatic skeleton.

  According to a third invention, in the general formula (1), X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom. It exists in the chain transfer agent which has the condensed polycyclic aromatic skeleton of description.

  A fourth invention is characterized in that, in the general formula (1), n is 4, R is a hydrogen atom, X is a hydroxy group or a methyl group, and Y is a hydrogen atom. The chain transfer agent having a condensed polycyclic aromatic skeleton described in the invention.

  A fifth invention is characterized in that, in the general formula (1), n is 4, R is a hydrogen atom, X is a chlorine atom, and Y is a chlorine atom or an amino group. The chain transfer agent having a condensed polycyclic aromatic skeleton described in the invention.

  The sixth invention resides in a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (2) or (3).

(In the formula (2), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.)

A seventh invention resides in a radically polymerizable composition comprising a chain transfer agent having a condensed polycyclic aromatic skeleton and a radically polymerizable compound described in any one of the first to sixth inventions. .

The eighth invention resides in the radical polymerizable composition according to the seventh invention, wherein the radical polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene.

A ninth invention is a polymer obtained by radical polymerization of the radically polymerizable composition according to the seventh invention or the eighth invention, wherein the condensed polycyclic ring is formed at the terminal of the polymer or a part of the main chain. It exists in a polymer having a residue derived from a chain transfer agent having an aromatic skeleton.

A tenth invention is characterized in that radical polymerization is performed on a radically polymerizable compound in the presence of a chain transfer agent having a condensed polycyclic aromatic skeleton described in any one of the first to sixth inventions. The present invention relates to a method for producing a polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton at a terminal of the polymer or a part of the main chain.

In the present invention, (meth) acryl represents acryl or methacryl, and (meth) acrylate represents acrylate or methacrylate.

By using the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention as a radically polymerizable compound, it is possible to effectively adjust the molecular weight of the desired polymer, and also the generation of unpleasant odors in the produced polymer. Can be suppressed. Furthermore, by polymerizing a radical polymerizable compound using the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention, the terminal or part of the main chain is derived from the chain transfer agent having a condensed polycyclic aromatic skeleton. A polymer having a residue can be synthesized.

It is a ^{1 H-NMR} spectrum of the polymer produced in Example 7 using 1,4-naphthoquinone as a chain transfer agent having a condensed polycyclic aromatic skeleton. The polymer produced in Example 7 was dissolved in deuterated chloroform, and ¹ H-NMR spectrum was measured using ECS-400 manufactured by JEOL.

[Chain transfer agent]
The chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is represented by general formulas (1) to (3).

(In the formula (1), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an amino group, or a halogen, but X and Y are bonded to each other instead of the substituent, and are a saturated or unsaturated 6-membered ring. The 6-membered ring formed by X and Y may be further substituted with an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom.)

(In the formula (2), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.)

In general formula (1) thru | or (3), as an alkyl group represented by R, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl Group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. As the aryl group, phenyl group, p-tolyl group, o-tolyl group, naphthyl Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and i. -A propoxy group etc. are mentioned, A phenoxy group, a triloxy group etc. are mentioned as an aryloxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In the general formulas (2) and (3), examples of the alkyl group represented by Q include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, and the like. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group represented by X and Y in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a pentyl group, 2- Examples include an ethylhexyl group, a 4-methylpentyl group, a 4-methyl-3-pentenyl group, and the alkoxy group includes a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and the like. Includes fluorine, chlorine, bromine and iodine.

In the general formula (1), as an example in which X and Y are bonded to each other, X and Y are CH ₂ CH ₂ groups, and X and Y are bonded by a single bond. It is represented by Formula (3). The compound in which X and Y are CH ₂ CH groups, and X and Y are bonded by a double bond, this compound is represented by the general formula (2). And X and Y are CH═CH groups, and X and Y are bonded by a single bond to form an aromatic ring. The 6-membered ring formed by X and Y may be further substituted with an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. Furthermore, examples of the substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group, and the aryl group includes a phenyl group. Group, p-tolyl group, o-tolyl group, naphthyl group, and the like. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, and the like. Methoxy group, ethoxy group, n-propoxy group, i-propoxy group and the like. Examples of the aryloxy group include a phenoxy group and a triloxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Next, specific examples of the compound represented by the general formula (1) will be given. First, in the general formula (1), examples of the compound in which X and Y are hydrogen atoms include the following compounds. For example, 1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6,7-dimethyl-1,4-naphthoquinone, 5-butyl-1,4-naphthoquinone, 6-butyl-1,4-naphthoquinone, 6,7-dibutyl-1,4-naphthoquinone, 5-pentyl-1,4-naphthoquinone, 6-pentyl-1,4-naphthoquinone, 5-chloro-1,4- Naphthoquinone, 6-chloro-1,4-naphthoquinone, 6,7-dichloro-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 6-hydroxy-1,4-naphthoquinone, 5,8-dihydroxy- 1,4-naphthoquinone, 5,6,8-trihydroxy-1,4-naphthoquinone, 5-methoxy-1,4-naphthoquinone, 6-methoxy-1,4-naphthoquinone 5,8-dimethoxy-1,4-naphthoquinone and the like.

Among these compounds, 1,4-naphthoquinone is easily available as a reagent. The compounds having substituents at the 5th to 8th positions are the corresponding naphthalenes as described in the 5th edition, Experimental Chemistry Lecture 15, Synthesis of Organic Compounds III Aldehyde, Ketone, and Quinone (edited by the Chemical Society of Japan), page 379. Oxidation treatment of compounds, as well as 5th edition Experimental Chemistry Course 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan), page 393 Cycloadducts can be synthesized by Alder reaction, then isomerized and oxidized.

Among these compounds, 1,4-naphthoquinone is particularly preferable because it is easy to produce and highly active.

Next, in the general formula (1), examples of the compound in which X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom include the following compounds. For example, 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 2-chloro-1,4- Naphthoquinone, 2-amino-1,4-naphthoquinone, 2,5-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-1,4-naphthoquinone, 2,6,7-trimethyl-1,4-naphthoquinone, 2-methyl-5-butyl-1,4-naphthoquinone, 2-methyl-6-butyl-1,4-naphthoquinone, 2-methyl-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-5 Pentyl-1,4-naphthoquinone, 2-methyl-6-pentyl-1,4-naphthoquinone, 2-methyl-5-chloro-1,4-naphthoquinone, 2-methyl-6-chloro-1,4-naphth Quinone, 2-methyl-6,7-dichloro-1,4-naphthoquinone, 2-methyl-5-hydroxy-1,4-naphthoquinone, 2-methyl-6-hydroxy-1,4-naphthoquinone, 2-methyl- 5,8-dihydroxy-1,4-naphthoquinone, 2-methyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2-methyl-5-methoxy-1,4-naphthoquinone, 2-methyl-6 -Methoxy-1,4-naphthoquinone, 2-methyl-5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-5-methyl-1,4-naphthoquinone, 2-ethyl-5-methyl-1,4 -Naphthoquinone, 2-ethyl-6-methyl-1,4-naphthoquinone, 2-ethyl-6,7-dimethyl-1,4-naphthoquinone, 2-ethyl-5-butyl-1,4-naphthoquino 2-ethyl-6-butyl-1,4-naphthoquinone, 2-ethyl-6,7-dibutyl-1,4-naphthoquinone, 2-ethyl-5-pentyl-1,4-naphthoquinone, 2-ethyl-6 -Pentyl-1,4-naphthoquinone, 2-ethyl-5-chloro-1,4-naphthoquinone, 2-ethyl-6-chloro-1,4-naphthoquinone, 2-ethyl-6,7-dichloro-1,4 -Naphthoquinone, 2-ethyl-5-hydroxy-1,4-naphthoquinone, 2-ethyl-6-hydroxy-1,4-naphthoquinone, 2-ethyl-5,8-dihydroxy-1,4-naphthoquinone, 2-ethyl -5,6,8-trihydroxy-1,4-naphthoquinone, 2-ethyl-5-methoxy-1,4-naphthoquinone, 2-ethyl-6-methoxy-1,4-naphthoquinone, 2-ethyl- 5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-6-methyl-1,4-naphthoquinone, 2-hydroxy-6,7-dimethyl-1,4-naphthoquinone, 2-hydroxy-5-butyl- 1,4-naphthoquinone, 2-hydroxy-6-butyl-1,4-naphthoquinone, 2-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-hydroxy-5-pentyl-1,4-naphthoquinone, 2-hydroxy-6-pentyl-1,4-naphthoquinone, 2-hydroxy-5-chloro-1,4-naphthoquinone, 2-hydroxy-6-chloro-1,4-naphthoquinone, 2-hydroxy-6,7- Dichloro-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2,6-dihydroxy-1,4-naphthoquinone, 2,5,8-toe Hydroxy-1,4-naphthoquinone, 2,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-hydroxy-5-methoxy-1,4-naphthoquinone, 2-hydroxy-6-methoxy-1,4 -Naphthoquinone, 2-hydroxy-5,8-dimethoxy-1,4-naphthoquinone, 2-methoxy-5-methyl-1,4-naphthoquinone, 2-methoxy-6-methyl-1,4-naphthoquinone, 2-methoxy -6,7-dimethyl-1,4-naphthoquinone, 2-methoxy-5-butyl-1,4-naphthoquinone, 2-methoxy-6-butyl-1,4-naphthoquinone, 2-methoxy-6,7-dibutyl -1,4-naphthoquinone, 2-methoxy-5-pentyl-1,4-naphthoquinone, 2-methoxy-6-pentyl-1,4-naphthoquinone, 2-methoxy 5-chloro-1,4-naphthoquinone, 2-methoxy-6-chloro-1,4-naphthoquinone, 2-methoxy-6,7-dichloro-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1, 4-naphthoquinone, 2-methoxy-6-hydroxy-1,4-naphthoquinone, 2-methoxy-5,8-dihydroxy-1,4-naphthoquinone, 2-methoxy-5,6,8-trihydroxy-1,4 -Naphthoquinone, 2,5-dimethoxy-1,4-naphthoquinone, 2,6-dimethoxy-1,4-naphthoquinone, 2,5,8-trimethoxy-1,4-naphthoquinone, 2-chloro-5-methyl-1 , 4-naphthoquinone, 2-chloro-6-methyl-1,4-naphthoquinone, 2-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-chloro-5-butyl-1, 4-naphthoquinone, 2-chloro-6-butyl-1,4-naphthoquinone, 2-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-chloro-5-pentyl-1,4-naphthoquinone, 2- Chloro-6-pentyl-1,4-naphthoquinone, 2,5-dichloro-1,4-naphthoquinone, 2,6-dichloro-1,4-naphthoquinone, 2,6,7-trichloro-1,4-naphthoquinone, 2-chloro-5-hydroxy-1,4-naphthoquinone, 2-chloro-6-hydroxy-1,4-naphthoquinone, 2-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-chloro-5, 6,8-trihydroxy-1,4-naphthoquinone, 2-chloro-5-methoxy-1,4-naphthoquinone, 2-chloro-6-methoxy-1,4-naphthoquinone, 2-chloro-5 8-dimethoxy-1,4-naphthoquinone, 2-amino-5-methyl-1,4-naphthoquinone, 2-amino-6-methyl-1,4-naphthoquinone, 2-amino-6,7-dimethyl-1, 4-naphthoquinone, 2-amino-5-butyl-1,4-naphthoquinone, 2-amino-6-butyl-1,4-naphthoquinone, 2-amino-6,7-dibutyl-1,4-naphthoquinone, 2- Amino-5-pentyl-1,4-naphthoquinone, 2-amino-6-pentyl-1,4-naphthoquinone, 2-amino-5-chloro-1,4-naphthoquinone, 2-amino-6-chloro-1, 4-naphthoquinone, 2-amino-6,7-dichloro-1,4-naphthoquinone, 2-amino-5-hydroxy-1,4-naphthoquinone, 2-amino-6-hydroxy-1,4-naphthoquinone 2-amino-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-5,6,8-trihydroxy-1,4-naphthoquinone, 2-amino-5-methoxy-1,4-naphthoquinone, 2 -Amino-6-methoxy-1,4-naphthoquinone, 2-amino-5,8-dimethoxy-1,4-naphthoquinone and the like.

Although many of these naphthoquinone compounds having a substituent at the 2-position are available as reagents, a hydroquinone compound substituted at the 2-position by reaction of a 1,4-naphthoquinone compound with the corresponding nucleophile is used. Thereafter, it can be obtained by oxidation treatment. For example, Fifth Edition Experimental Chemistry Lecture 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan) pages 369 and 384 can be synthesized.

In general, a compound having a substituent at the 2-position of the naphthoquinone skeleton is easy to produce and is preferable. Among these compounds, 2-methyl-1,4-naphthoquinone and 2-hydroxy-1,4-naphthoquinone are: It is preferable because it is easy to produce and highly active.

Furthermore, in the general formula (1), examples of the compound in which X and Y are a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom include the following compounds. For example, 2,3-dimethyl-1,4-naphthoquinone, 2,3-diethyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-methoxy-1, 4-naphthoquinone, 2,3-dihydroxy-1,4-naphthoquinone, 2,3-dimethoxy-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro-1, 4-naphthoquinone, 2,3,6-trimethyl-1,4-naphthoquinone, 2,3,6,7-tetramethyl-1,4-naphthoquinone, 2,3-dimethyl-5-butyl-1,4-naphthoquinone 2,3-dimethyl-6-butyl-1,4-naphthoquinone, 2,3-dimethyl-6,7-dibutyl-1,4-naphthoquinone, 2,3-dimethyl-5-pentyl-1,4-naphthoquinone 2,3-dimethyl-6-pentyl-1,4-naphthoquinone, 2,3-dimethyl-5-chloro-1,4-naphthoquinone, 2,3-dimethyl-6-chloro-1,4-naphthoquinone, 2,3-dimethyl-6,7-dichloro-1,4-naphthoquinone, 2,3-dimethyl-5-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-6-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5-methoxy-1 , 4-naphthoquinone, 2,3-dimethyl-6-methoxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dimethoxy-1,4-naphthoquinone, 2,6-dimethyl-3-hydroxy- , 4-naphthoquinone, 2,6,7-trimethyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6 -Butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-pentyl-1,4-naphthoquinone, 2-methyl -3-hydroxy-6-pentyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-chloro-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-chloro-1,4-naphthoquinone 2-methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-methyl-3, 6-dihydroxy-1,4-naphthoquinone, 2-methyl-3,5,8-trihydroxy-1,4-naphthoquinone, 2-methyl-3,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5,8-dimethoxy- 1,4-naphthoquinone, 2,3-dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro-5-butyl- 1,4-naphthoquinone, 2,3-dichloro-6-butyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dibutyl-1,4-naphthoquinone, 2,3-dichloro-5-pen 1,4-naphthoquinone, 2,3-dichloro-6-pentyl-1,4-naphthoquinone, 2,3,5-trichloro-1,4-naphthoquinone, 2,3,6-trichloro-1,4- Naphthoquinone, 2,3,6,7-tetrachloro-1,4-naphthoquinone, 2,3-dichloro-5-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4-naphthoquinone 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dichloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dichloro-5-methoxy- 1,4-naphthoquinone, 2,3-dichloro-6-methoxy-1,4-naphthoquinone, 2,3-dichloro-5,8-dimethoxy-1,4-naphthoquinone, 2-amino-3-chloro-6 Me 1,4-naphthoquinone, 2-amino-3-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-amino-3-chloro-5-butyl-1,4-naphthoquinone, 2-amino- 3-chloro-6-butyl-1,4-naphthoquinone, 2-amino-3-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-amino-3-chloro-5-pentyl-1,4- Naphthoquinone, 2-amino-3-chloro-6-pentyl-1,4-naphthoquinone, 2-amino-3-chloro-5-chloro-1,4-naphthoquinone, 2-amino-3,6-dichloro-1, 4-naphthoquinone, 2-amino-3,6,7-trichloro-1,4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro-6 Hydroxy-1,4 -Naphthoquinone, 2-amino-3-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-3-chloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2-amino- 3-chloro-5-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-6-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-5,8-dimethoxy-1,4- And naphthoquinone.

Many of these naphthoquinone compounds having a substituent at the 2-position are available as reagents, but are obtained by repeating the oxidation treatment after the reaction between the 1,4-naphthoquinone compound and the corresponding nucleophile. be able to. For example, it can be synthesized by the method described in page 386 of Fifth Edition Experimental Chemistry Lecture 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan).

Among these compounds, 2,3-dichloro-1,4-naphthoquinone and 2-amino-3-chloro-1,4-naphthoquinone are preferable because they are easy to produce and highly active.

In the general formula (1), examples in which X and Y are bonded to each other include the following compounds. First, X and Y are CH ₂ CH groups, and X and Y are bonded by a double bond, and this compound is a compound represented by the general formula (2). 1,4-dihydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-1,4-dihydro-9,10-anthraquinone, 6-methyl-1 , 4-dihydro-9,10-anthraquinone, 2,6-dimethyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-6-methyl-1,4-dihydro-9,10-anthraquinone, 2 , 6-dichloro-1,4-dihydro-9,10-anthraquinone and the like. In addition, X and Y are CH ₂ CH ₂ groups and X and Y are bonded by a single bond, and this compound is a compound represented by the general formula (3). 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-1,2,3,4-tetrahydro- 9,10-anthraquinone, 6-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2,6-dimethyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2- Examples include chloro-6-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone and 2,6-dichloro-1,2,3,4-tetrahydro-9,10-anthraquinone. Furthermore, examples of the compound other than the compound represented by the general formula (2) or (3) in which X and Y are bonded to each other in the general formula (1) include 9,10-anthraquinone, 2- Methyl-9,10-anthraquinone, 2-chloro-9,10-anthraquinone, 6-methyl-9,10-anthraquinone, 2,6-dimethyl-9,10-anthraquinone, 2-chloro-6-methyl-9, Examples include 10-anthraquinone and 2,6-dichloro-9,10-anthraquinone.

These compounds synthesize cycloaddition products by Diels-Alder reaction of 1,4-naphthoquinone compounds and the corresponding butadiene compounds, then isomerize and then oxidize, and further catalytically reduce this oxidant with hydrogen. Can be synthesized.

Among these compounds, 1,4-dihydro-9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone 2-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-1,4-dihydro-9,10-anthraquinone, 2-chloro-1,2,3,4-tetrahydro -9,10-anthraquinone is preferred because it is easy to produce and highly active.

[Radically polymerizable composition]
By using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, the degree of polymerization of the radical polymerizable compound can be adjusted in the polymerization reaction of the radical polymerizable compound. The chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention can be used as a radical polymerizable composition by adding it to a radical polymerizable compound.

If necessary, a radical polymerization initiator for initiating a radical reaction is added to the radical polymerizable composition containing the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention as an essential component. A polymer having a molecular weight adjusted can be produced by applying initiation energy such as heat and light necessary for initiating the polymerization and initiating the polymerization.

The blending amount of the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is usually preferably 0.01 to 5% by weight based on the radical polymerizable compound from the viewpoint of sufficient chain transfer effect and economy. 0.05 to 3% by weight is more preferable.

[Radical polymerization]
As the polymerization method, various polymerization methods such as solution polymerization, emulsion polymerization and suspension polymerization can be employed. The solution polymerization method is usually performed using a solvent that uniformly dissolves a reagent such as a monomer or a radical polymerization initiator. Usually, it is selected based on physical chemical properties such as solubility in monomer, boiling point, freezing point, etc., and it is selected from the viewpoint of harmfulness, safety and environmental load depending on the intended use and usage. From such a viewpoint, aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon, alcohol, carboxylic acid, nitrile, ester, ketone, sulfoxide, water and the like can be mentioned. Aliphatic hydrocarbons are hexane, cyclohexane, aromatic hydrocarbons are toluene, xylene, halogenated hydrocarbons are chloroform, carbon tetrachloride, alcohol is ethanol, 1,4 butanediol, and carboxylic acid is acetic acid. Examples of propionic acid and nitrile include acetonitrile, examples of ester include ethyl acetate and butyl acetate, examples of ketone include methyl ethyl ketone, methyl isobutyl ketone, and sulfoxide include dimethyl sulfoxide. In addition, the solvents described in “Solvent Handbook” (Shozo Asahara et al., Kodansha Scientific, 1976) can be used. Usually, aromatic hydrocarbons having good solubility are preferably used. Toluene and xylene are particularly preferably used.

In the emulsion polymerization method, a hydrophobic monomer that is hardly soluble in water, such as vinyl acetate, styrene, and (meth) acrylate, and a radical polymerization initiator are usually used in the presence of a surfactant. The mixture is stirred and polymerized in an emulsified state (O / W emulsion). In that case, the polymerization degree etc. of a radically polymerizable compound can be adjusted by adding the chain transfer agent which has the condensed polycyclic aromatic skeleton of this invention.

In the emulsion polymerization method, a method (W / O type emulsion) in which a hydrophilic monomer that is hardly soluble in an organic solvent is polymerized in the presence of a radical polymerization initiator using an organic solvent as a medium is also used. By adding the chain transfer agent having the condensed polycyclic aromatic skeleton of the invention, the degree of polymerization of the radical polymerizable compound can be adjusted.

In the suspension polymerization method, for example, a hydrophobic monomer that is hardly soluble in water, such as vinyl acetate, styrene, and (meth) acrylic acid ester, and a radical polymerization initiator are mixed and stirred in water using a dispersion stabilizer. Polymerizes in suspension. In that case, the polymerization degree etc. of a radically polymerizable compound can be adjusted by adding the chain transfer agent which has the condensed polycyclic aromatic skeleton of this invention.

As a dispersion for creating a suspended state, sodium hydroxide is added to an aqueous magnesium chloride solution to prepare a magnesium hydroxide colloidal dispersion. A polymerizable compound is added to the dispersion to disperse it, and a radical polymerization initiator and Suspension polymerization can also be carried out by adding a chain transfer agent.

Further, an aqueous solution of a water-soluble ethylenically unsaturated monomer such as acrylic acid and its alkali metal salt, methacrylic acid and its alkali metal salt, acrylamide, methacrylamide and N, N-dimethylacrylamide is used as a surfactant, radical There is also a reverse phase suspension polymerization method in which a polymerization initiator, a crosslinking agent and an organic solvent are mixed, heated with stirring, and polymerized in a water-in-oil system. Also in that case, the degree of polymerization of the radical polymerizable compound can be adjusted by adding the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention.

[Method of adding chain transfer agent]
The method for adding the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention to the polymerization reactor is not particularly limited, but is a method of mixing from the beginning with a radical polymerizable compound to form a radical polymerizable composition, polymerization Known additions such as a method of batch addition to the reaction system at the time of reaction, a method of batch addition in each step or several times depending on the degree of polymerization, a method of continuous addition at a set time, or a combination thereof The method is selected according to its purpose.

The form of adding the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention to the polymerization reactor is a method of directly adding the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention as a solid or powder. Or a method of adding the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention after dissolving it in water or a suitable organic solvent or making it into a slurry, or a radical polymerizable compound and the condensed polycyclic aromatic skeleton of the present invention You may adjust and add what mixed the chain transfer agent which has.

The number average molecular weight of the polymer can be adjusted by the concentration of the radically polymerizable compound generally used, the concentration of the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, and the concentration of the radical polymerization initiator. For example, the greater the blending amount of the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention relative to the radical polymerizable compound, the smaller the number average molecular weight, and conversely, the smaller the blending amount, the greater the number average molecular weight. . In view of this, the number average molecular weight can be adjusted by appropriately changing the concentration within the range of the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention.

[Radically polymerizable compound]
The radically polymerizable compound in the present invention is not particularly limited as long as it is a compound having a polymerizable double bond in the molecule. Examples of such radically polymerizable compounds include α, β-unsaturated carboxylic acid compounds such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Α, β-unsaturated carboxylic acid ester compounds such as octyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate; vinyl ester compounds such as vinyl acetate; acrylonitrile, Acrylic compounds such as acrylamide; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and divinylbenzene; substituted ethylene compounds such as vinyl chloride and vinylidene chloride; ethylene, propylene, butene, butadiene, isoprene, cyclo Pentadie And unsaturated organic silane compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and vinyltrimethoxysilane. These radically polymerizable compounds may be used alone or in combination of two or more.

Among the radical polymerizable compounds, α, β-unsaturated carboxylic acid compounds, α, β-unsaturated carboxylic acid ester compounds, aromatic vinyl compounds, vinyl ester compounds, or combinations thereof are preferable.

Among these compounds, (meth) acrylic acid which is an α, β-unsaturated carboxylic acid compound, (meth) acrylic ester which is an α, β-unsaturated carboxylic acid ester, styrene which is an aromatic vinyl compound, α -Methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate which is a vinyl ester compound or a combination thereof is preferred. In particular, styrene, (meth) acrylic acid ester, vinyl acetate, or a combination thereof is preferable because the effect of the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is remarkable.

The form and content of the radical polymerizable compound contained in the radical polymerizable composition are not particularly limited. For example, a radical polymerizable compound itself or a solution of a radical polymerizable compound can be used.

[Radical polymerization initiator]
The radical polymerization initiator is not particularly limited as long as it gives energy and generates an active radical for the radical polymerizable compound. Generally, so-called radical polymerization initiators that are commercially available can be used. For convenience, what is used with thermal energy applied is called a thermal radical polymerization initiator, and what gives light energy is called a photo radical polymerization initiator. In the present invention, both a thermal radical polymerization initiator and a photo radical polymerization initiator can be used.

It does not specifically limit as a thermal radical polymerization initiator, A well-known compound can be used. For example, a peroxide, a hydroperoxide, and an azo compound are mentioned. Specifically, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, benzoyl peroxide, di-t-amyl peroxide, t-butylperoxybenzoate, 2,5-dimethyl-2,5 di- (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, t-butylperoxy 2-ethylhexanoate (perbutyl O, "perbutyl" (Registered trademark) 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Perocta O, “Perocta” is a registered trademark of NOF Corporation), t-hexylperoxy 2-ethylhexanoate ( Perhexyl O, “Perhexyl” is a registered trademark of NOF Corporation) and peroxides such as di-cumyl peroxide, t-amyl hydroperoxide t-butyl hydroperoxide and hydroperoxides such as hydrogen peroxide, (2,2′-azobis (2,4-dimethylpentanenitrile)), (2,2′-azobis (2-methylpropanenitrile)), ( And azo compounds such as (2,2′-azobis (2-methylbutanenitrile)) and (2,2′-azobis (cyclohexanecarbonitrile)).

In addition, in order to use a thermal radical polymerization initiator at a relatively low temperature, a so-called redox initiator system is used in which a reducing agent such as a transition metal or an amine is combined with an oxidizing initiator such as peroxide, hydroperoxide, or ascorbic acid. You can also

It does not specifically limit as radical photopolymerization initiator, A well-known compound can be used. For example, benzoin compounds, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, organic dye compounds , Iron-phthalocyanine series, benzoins, benzoin ethers, anthraquinones. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- Acetophenones such as 2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthate Thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Photo radical polymerization initiators introduced in known literature such as Journal of Synthetic Organic Chemistry 66, 458 (2008) can also be used.

Further, as a photo radical polymerization initiator available from the market, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals, Inc., Irgacure is a registered trademark of Ciba Specialty Chemicals), (2-methyl-1- ( Acylphosphines such as 4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propanone) (Irgacure 907) and bis (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide (Irgacure 819) Oxide compounds; titanocenes such as bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784) Compound; 6,12-bis (trimethylsilane And naphthacenequinone compounds such as ryloxy) -1,11-naphthacenequinone.

These radical polymerization initiators may be used alone or in combination of two or more. The amount of radical polymerization initiator added depends on the radical polymerizable compound and chain transfer agent used, but within a range of 0.0001 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable compounds. Preferably there is.

[Starting energy]
The starting energy may be any energy that can generate radicals from the added radical initiator. In general, thermal energy and ionization wave energy are appropriately selected. Specific examples of the energy source include heat, light, electron beam (EB), microwave, radiation and other electromagnetic rays. Depending on the energy source used, thermal polymerization, electromagnetic ray polymerization (photopolymerization, electron beam polymerization, Microwave polymerization, radiation polymerization) and the like.

In the case of thermal polymerization, although it depends on the polymerizable compound used and its mode, the temperature range used for the polymerization is usually -20 to 200 ° C, preferably 0 to 150 ° C, more preferably 10 to 120 ° C.

Furthermore, redox polymerization using a redox (redox) initiator (described later) is one type of thermal polymerization. Under the present circumstances, the temperature range used is lower than normal thermal polymerization, is -40-100 degreeC, Preferably it is -20-80 degreeC, More preferably, it is 0-60 degreeC.

In photopolymerization, ultraviolet light, visible light, infrared light, or the like can be used as light to be irradiated. A radical photopolymerization initiator or a sensitizer can also be used. In the case of ultraviolet rays and visible rays, specifically, for example, rays in the wavelength range of 300 to 800 nm. As the light source, an LED (light emitting diode) or a lamp that can irradiate light having a wavelength in the range of 300 to 800 nm is used. Examples of the LED include a UV-LED, a blue LED, and a white LED. Examples of the lamp include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, and a metal halide lamp.

Electron beam polymerization is performed by electron beam irradiation. For the electron beam irradiation, any method that can act on the electron beam polymerization compound and cause polymerization of the polymerizable substance can be used without particular limitation. The electron dose to be irradiated is preferably adjusted in the range of about 1 to 300 kGy as an absorbed dose. If it is less than 1 kGy, sufficient irradiation effect cannot be obtained, and irradiation exceeding 300 kGy is not preferable because there is a possibility of deteriorating the substrate. As an electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like is used, and the acceleration voltage when irradiating the electron beam needs to be controlled by the thickness of the substrate on the irradiation side. However, about 20 to 100 kV is appropriate.

For the microwave polymerization, a known method of Strauss et al. (Aust. J. Chem., 48, 1665-1692 (1995)) can be used. Microwaves can be generated by any of a variety of methods known in the microwave arts. In general, these methods rely on a klystron or magnetron acting as a microwave source. In general, the frequency of occurrence is in the range of about 300 MHz to 30 GHz and the corresponding wavelength is about 1 m to 1 mm. Theoretically, any frequency in this range can be used effectively, but it is preferred to use a commercially available range of frequencies, including about 850-950 MHz or about 2300-2600 MHz. .

Radiation polymerization is carried out by irradiating γ rays, X rays, α rays, and β rays. Usually, γ-ray irradiation of cobalt 60 is often used.

Furthermore, an energy source for initiating polymerization can be used in combination. For example, an electron beam and infrared rays are used together.

In addition to the thermal polymerization, the polymerization is usually carried out at around room temperature, but it can also be carried out while heating. In this case, acceleration of polymerization can be expected.

[Other ingredients]
In radical polymerization of a radical polymerizable composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention and a radical polymerizable compound, a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention, a radical If necessary in addition to the polymerizable compound and the radical polymerization initiator, other components may be contained within a range not impairing the effects of the present invention. In addition to the components exemplified below, a colorant, a plasticizer, It is also possible to add tackifiers, antioxidants, various stabilizers, fillers, antistatic agents, ultraviolet absorbers, fungicides, antiseptics, antibacterial agents, deodorants and the like.

For example, the surfactant is not particularly limited as long as it is a known surfactant. For example, alkyl sulfate ester salts, alkylaryl sulfonate salts, sulfosuccinate ester salts, fatty acid salts, polyoxyethylene alkylaryl Anionic surfactants such as sulfate ester salts and polyoxyethylene alkyl sulfate ester salts (herein, “salts” include potassium salt, sodium salt, ammonium salt, etc.), sorbitan esters, polyoxyethylene Examples thereof include hydrophilic nonionic surfactants such as alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl esters. Any one of these may be used alone or two or more of them may be used in combination.

In the emulsion polymerization, as an emulsifier, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, ester of sodium sulfosuccinate, Abex anionic surfactant (Alcolac), alkylphenoxypolyethoxyethanol (HLB = 13 to 19), block copolymers of ethoxy fatty acid alcohol (HLB = 13 to 19), ethylene oxide and propylene oxide, and the like.

In addition, a water-soluble protective colloid may be used in the emulsion polymerization. Representative examples of such protective colloids include hydroxyethyl cellulose, poly (ethylene oxide-propylene oxide) polyvinyl alcohol, polyethylene oxazoline, polyvinyl pyrrolidone (PVP), and copolymers of the above compounds. The protective colloid is usually used in a proportion of 0.1 to 1.5% by weight with respect to the monomer.

In suspension polymerization, a dispersion stabilizer can also be used. Examples of the dispersion stabilizer include water-soluble or oil-soluble partially saponified polyvinyl alcohol; water-soluble cellulose such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose; acrylic acid polymer, methyl vinyl ether-maleic anhydride Water-soluble polymers such as polymers, styrene-maleic anhydride copolymers, gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan monostearate, glycerin monostearate, ethylene oxide propylene oxide block copolymers, polyoxyethylene sorbitan Water-soluble emulsifiers such as monolaurate, polyoxyethylene glycerine oleate, and sodium laurate are mentioned, and these are one kind or a combination of two or more kinds. It can be used.

In addition, upon polymerization, the reaction system includes starch / cellulose, starch / cellulose derivatives, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) cross-linked hydrophilic polymer 0 to 50% by weight ( Monomers) and other 0 to 10% by weight of various foaming agents such as carbonic acid (hydrogen) salts, carbon dioxide, azo compounds, inert organic solvents; chelating agents; inorganic fine particles such as kaolin, talc and silicon dioxide A polyvalent metal salt such as polyaluminum chloride, aluminum sulfate, and magnesium sulfate may be added.

Moreover, in the range which does not impair the effect of this invention, you may contain components, such as chain transfer agents other than the chain transfer agent which has the condensed polycyclic aromatic skeleton of this invention. Such other chain transfer agents are not particularly limited, and examples include known compounds as chain transfer agents.

For example, mercaptans such as n-butyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, disulfides such as tetramethylthiudium disulfide, tetraethylthuradium disulfide, carbon tetrachloride, Examples thereof include halogen compounds such as carbon tetrabromide, and olefins such as 2-methyl-1-butene and α-methylstyrene dimer.

These other components can be used alone or in combination of two or more kinds with the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. These other components can be appropriately selected according to the type and application of the radical polymerizable compound to be applied.

<Manufacturing mode>
By radical polymerization of a radical polymerizable composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention and a radical polymerizable compound, the end of the polymer to be produced or a part of the main chain is condensed. A polymer having a residue derived from a chain transfer agent having a ring aromatic skeleton can be produced.

As a production mode of a polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton at a polymer terminal or a part of the main chain, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, or slurry A method such as polymerization can be used. Moreover, it can be used even when polymerizing batchwise or continuously.

The atmosphere during the polymerization preferably removes molecular oxygen and is generally used under reduced pressure or in the presence of an inert gas. Examples of the inert gas include nitrogen, argon, helium, carbon dioxide and the like.

<Polymer having condensed polycyclic aromatic skeleton at terminal>
The polymer produced by the above polymerization method using the chain transfer agent of the present invention is a condensed polycyclic aromatic which is a residue derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention at the terminal as described above. It is possible to impart a skeleton. That is, the chain transfer agent of the present invention has a terminal structure derived from the chain transfer agent because it is added to the polymer growth terminal and chain-transferred. Therefore, it is possible to synthesize a polymer having a residue derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention at the terminal, and further to the functionality of the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. Groups can be imparted to the polymer. Generates the chemical and physical properties of the condensed polycyclic aromatic skeleton and functional groups, such as affinity, reactivity, heat resistance, optical properties, and chemical stability, derived from the condensed polycyclic aromatic skeleton and functional groups It can be applied to a polymer and used as a functional polymer.

That is, the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention can provide a terminal functionalized polymer having a reactive group.

For example, by using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, the condensed polycyclic aromatic skeleton is introduced into the polymer. Properties such as properties and high refractive index can be imparted to the polymer. Further, by using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, a hydrophobic group is introduced into the terminal of the polymer, or a group having both a hydrophilic group and a hydrophobic group is introduced. Can do.

In general, it is well known that radicals are generated through a decomposition reaction by applying heat, light, mechanical energy, etc. to a polymer (Takayuki Otsu, “Chemistry of Polymer Synthesis” (Chemical Doujin, 1979), page 245, 250, 260). At that time, by applying the chain transfer agent of the present invention, it is possible to prevent gelation of the polymer or to graft a functional group. For example, methods described in JP-A-54-100449, JP-A-6-256430 and the like can be used. Specifically, a thermoplastic polymer is melt-kneaded to give thermal energy and mechanical energy, and while cutting the polymer chain, the chain transfer agent of the present invention is applied as an additive to prevent polymer gelation. , Functional groups can be grafted.

Example 1
4 g of commercially available styrene (Wako special grade) as a radical polymerizable compound is put in a test tube, 1% by mass of azobisisobutyronitrile (Wako special grade), chain transfer as a radical polymerization initiator for this radical polymerizable compound. 500 mass ppm of 1,4-naphthoquinone was added as an agent to form a radically polymerizable composition. The test tube containing the radical polymerizable composition was capped with a septum, and nitrogen was bubbled through the composition at a rate of 15 mL / min for 20 minutes. Then, the test tube was immersed in a heated oil bath while the nitrogen was being passed, and the solution temperature in the test tube was kept at 60 ° C. for 5 hours, which was used as the polymerization time. The product is dissolved in tetrahydrofuran (Wako Special Grade) at a predetermined concentration, and a refractometer (RI) (manufactured by JASCO RI-2031), a multiwavelength ultraviolet spectrometer (manufactured by JASCO MD-2010), and GPC are used as detectors. The produced polymer was characterized using gel permeation chromatography (manufactured by JASCO) equipped with a column (Showex DPC Shodex GPC KF-806L). Among these, a refractometer was used as a detector, and the polymerization rate was measured from the average molecular weight of the produced polymer, its distribution and its peak area. Furthermore, using a multi-wavelength ultraviolet spectrometer as a detector, the ultraviolet absorption spectrum of the produced polymer was measured, and the presence or absence of absorption at a wavelength of 350 to 500 nm derived from the condensed polycyclic aromatic skeleton was measured. These measurement results are shown in Table 1.

(Examples 2 to 20, Comparative Examples 1 to 6)
The same procedure as in Example 1 was performed except that the type of chain transfer agent to be added, the amount of chain transfer agent added, the radical polymerizable compound, and the polymerization time were changed as shown in Table 1, and the measurement results are shown in Table 1 and It is shown in Table 2.

(Example 21) Emulsion polymerization (collective addition of radically polymerizable compounds)
75 parts (3.125 g) of commercially available styrene (Wako Special Grade) as a radical polymerizable compound and 25 parts (9.375) g of commercially available n-butyl acrylate (Tokyo Kasei), 1,4-naphthoquinone 0 as a chain transfer agent 0.8 parts (0.1 g), 2 parts (0.25 g) sodium dodecylbenzenesulfonate as a surfactant and 400 parts (100 g) deionized water in a condenser, stirring blade, thermometer, temperature controller, nitrogen supply The mixture was added to a 300 mL separable flask equipped with a line, stirred for 3 minutes, and then subjected to ultrasonic wave for 5 minutes to obtain a dispersion. Further, 2 parts (0.25 g) of ammonium persulfate as a radical polymerization initiator was added to 20 parts (2.5 g) of deionized water to prepare a radical polymerization initiator aqueous solution. Nitrogen was bubbled through the flask containing the dispersion at a rate of 20 mL / min for 20 minutes, and the inside of the flask was purged with nitrogen. Then, 6.25 parts (0.6875 g) of a radical polymerization initiator aqueous solution was added, and the temperature of the dispersion was It was held for 6 hours to reach 90 ° C. During this period, 6.25 parts (0.6875 g) of radical polymerization initiator aqueous solution was further added at 1, 2, and 3 hours. After the completion of the polymerization reaction, the polymerization product is dissolved in tetrahydrofuran (Wako Special Grade) at a predetermined concentration, and as a detector, a refractometer (RI) (JASCO RI-2031), a multi-wavelength ultraviolet spectrometer (JASCO MD) -2010), and gel permeation chromatography (manufactured by JASCO Corporation) equipped with a GPC column (Shodex GPC KF-806L manufactured by Showa Denko) was used to characterize the produced polymer. Among these, a refractometer was used as a detector, and the polymerization rate was measured from the average molecular weight of the produced polymer, its distribution and its peak area. Furthermore, using a multi-wavelength ultraviolet spectrometer as a detector, the ultraviolet absorption spectrum of the produced polymer was measured, and the presence or absence of absorption at a wavelength of 350 to 500 nm derived from the condensed polycyclic aromatic skeleton was measured. The measurement results are shown in Table 3.

(Example 22) Emulsion polymerization (continuous addition of radically polymerizable compound)
75 parts (12.875 g) of commercially available styrene (Wako Special Grade) as a radically polymerizable compound to be continuously added and 25 parts (4.0625 g) of commercially available n-butyl acrylate (Tokyo Kasei), 1,4-as a chain transfer agent A solution in which 0.8 part (1.3 g) of naphthoquinone was mixed was used as a monomer mixed solution. Meanwhile, 2 parts (0.325 g) of ammonium persulfate was added to 114 parts (18.5 g) of deionized water to prepare a radical polymerization initiator aqueous solution. Then, a 300 mL separable flask equipped with a condenser, a stirring blade, a thermometer, a temperature controller, a nitrogen supply line, a monomer mixture supply line from the liquid feed pump, and an initiator aqueous solution supply line from the liquid feed pump was connected to the interface. As an activator, 2 parts (3.25 g) of sodium dodecylbenzenesulfonate and 686 parts (111.8 g) of deionized water were added to prepare a dispersion. Nitrogen was bubbled through the flask containing the dispersion at a rate of 20 mL / min for 20 minutes to replace the inside of the flask with nitrogen, and the temperature of the dispersion was increased to 90 ° C. After the liquid temperature of the dispersion reached 90 ° C., the monomer mixed solution and the radical polymerization initiator aqueous solution were added dropwise at a flow rate of 0.31 mL / min for 1 hour. After completion of the dropwise addition, the liquid temperature of the dispersion was kept at 90 ° C. for 3 hours. The product was characterized by gel permeation chromatography as in emulsion polymerization. The measurement results are shown in Table 3.

(Comparative Example 7)
The same operation as in Example 21 was performed except that the chain transfer agent was not added, and the measurement results are shown in Table 3.

(Comparative Example 8)
The same operation as in Example 22 was performed except that the chain transfer agent was not added, and the measurement results are shown in Table 3.

(Example 23) Suspension polymerization (collective addition of radically polymerizable compounds)
In a 300 mL separable flask equipped with a condenser, stirring blade, thermometer, temperature controller and dropping funnel nitrogen supply line, 250 parts (125 g) of deionized water and 10.2 parts (5.1 g of magnesium chloride hexahydrate) ) Was added. Nitrogen was bubbled through the flask at a rate of 20 mL / min for 20 minutes to purge the interior of the flask with nitrogen. A 12.4 wt% sodium hydroxide solution in which 6.2 parts (3.1 g) of sodium hydroxide was added to 50 parts (25 g) of deionized water was dropped from the dropping funnel to prepare a dispersion. In this dispersion, 76 parts (19 g) of commercially available styrene (19 g) as a radical polymerizable compound, 24 parts (6 g) of commercially available n-butyl acrylate (Tokyo Kasei) and 1 part of 1,4-naphthoquinone as a chain transfer agent (0.25 g) of the mixed solution was dropped with a dropping funnel. Then, 4.4 parts (0.25 g) of perbutyl O (t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation)) was added as a radical polymerization initiator, and the dispersion was immediately brought to 90 ° C. The temperature was raised and held for 6 hours. During this time, 0.2 part (0.05 g) of 1,4-naphthoquinone was sequentially added a total of 12 times at 30 minute intervals. Thereafter, the dispersion was cooled with ice water to stop the polymerization reaction. For neutralization of the dispersion, a small amount of sulfuric acid was added to neutralize the pH to 5-6. Thereafter, stirring was stopped, suction filtration was performed with No. 5C KIRIYAMA filter paper, and the polymer was washed with a small amount of water. The polymer washed with water was dried under reduced pressure, and the resulting product was characterized using gel permeation chromatography in the same manner as emulsion polymerization. The measurement results are shown in Table 3.

(Comparative Example 9)
The same operation as in Example 23 was performed except that the chain transfer agent was not added, and the measurement results are shown in Table 3.

(Example 24) Commercially available toluene (Wako special grade) 100 parts (60 g) and commercial styrene (Wako special grade) in a 300 mL separable flask equipped with a solution polymerization condenser, stirring blade, thermometer, temperature controller and nitrogen supply line ) 100 parts (60 g), 1,4-naphthoquinone 0.5 part (0.3 g) as a chain transfer agent, 1 part (0.6 g) azobisisobutyronitrile (Wako special grade) as a radical polymerization initiator Nitrogen was bubbled through the flask at a rate of 20 mL / min for 20 minutes to replace the inside of the flask with nitrogen. Thereafter, the liquid temperature was raised to 60 ° C. and held for 6 hours. The resulting polymer solution was characterized using gel permeation chromatography. The measurement results are shown in Table 3.

(Comparative Example 10)
The same operation as in Example 24 was performed except that the chain transfer agent was not added, and the measurement results are shown in Table 3.

From the above results, the following is clear. That is, from the comparison of Example 1 to Example 7, Example 9 to Example 20, and Comparative Examples 1, 5, and 6, the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention is remarkably produced. It can be seen that the average molecular weight (Mn) is lowered and the chain transfer ability is excellent. Further, from comparison between Example 1 to Example 19 and Comparative Example 2 using α-methylstyrene dimer which is a conventionally known chain transfer agent, the chain having the condensed polycyclic aromatic skeleton of the present invention is used. It can be seen that the transfer agent reduces the number average molecular weight (Mn) of the produced polymer to the same or higher level than the α-methylstyrene dimer, and has excellent chain transfer ability.

Further, as can be seen from the comparison with Comparative Examples 3 and 4 using benzoquinone, benzoquinone has the ability to inhibit polymerization but has no chain transfer ability, or the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. It can be seen that it is very low compared to. That is, when Examples 1 and 2 are compared with Comparative Example 4, when benzoquinone is used and when a 1,4-naphthoquinone compound that is a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is used, Although the average molecular weight is a close value, it can be seen that the polymerization rate at that time is extremely low when benzoquinone is used. Also, the molecular weight distribution is a large value in the example using benzoquinone. That is, it can be seen that the chain transfer effect of benzoquinone is low and it works as a polymerization inhibitor. As described above, the effect as a chain transfer agent varies greatly depending on the quinone structure, and is not a general function of a quinone structure but a function specific to the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. I understand.

And in Examples 1-20 using the chain transfer agent which has the condensed polycyclic aromatic skeleton of this invention, in the ultraviolet absorption spectrum of the produced | generated polymer, absorption in wavelength 350-500nm is observed, and FIG. In the ¹ H-NMR spectrum of the polymer obtained in Example 7 shown above, a peak derived from the proton of the naphthalene skeleton was observed at δ = 7.5 to 8 together with the spectrum of the polystyrene skeleton. It can be seen that the condensed polycyclic aromatic skeleton derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention is introduced into the polymer.

Furthermore, from the comparison between Examples 21 and 22 and Comparative Examples 7 and 8, the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention significantly reduces the number average molecular weight (Mn) of the produced polymer even in emulsion polymerization. It can be seen that it has excellent chain transfer ability. Furthermore, from the comparison between Example 23 and Comparative Example 9, it can be seen that the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention also has excellent chain transfer ability in suspension polymerization. Furthermore, from the comparison between Example 24 and Comparative Example 10, it can be seen that the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention has excellent chain transfer ability also in solution polymerization.

(Example 25) Use of synthetic polymer (synthesis of prepolymer 1)
Synthesis of 4- (6-isocyanatohexylcarbamoyloxy) -naphthalen-1-yl- (6-isocyanatohexyl) carbamate In a 100 ml reaction vessel equipped with a stirrer etc. under nitrogen atmosphere 3 mmol) and 0.1 g (1 mmol) of triethylamine were charged and ice-cooled. Next, 3.2 g (20.1 mmol) of 1,4-naphthalenediol was dissolved in 7 ml of tetrahydrofuran and slowly dropped with a syringe over 2 to 3 minutes, and the syringe was further washed with 3 ml of tetrahydrofuran and added. At this point, the reaction was started, and the reaction solution immediately became a slurry of white crystals. The reaction was continued by cooling with ice, and stirring became difficult with a slurry solution containing a large amount of crystals in about 10 minutes from the start. 30 minutes after the start, 100 ml of n-hexane was added and stirred, and then the crystals were separated by suction filtration and washed several times with n-hexane. The product was a white solid, and the amount obtained after vacuum drying was 9.1 g (yield 91 mol%). The product after drying is designated as Prepolymer 1.

The prepolymer 1 as a reaction product had the following composition distribution when 1,4-naphthalenediol was A and hexamethylene diisocyanate was B.
Composition distribution: a mixture of B-A-B, B-A-B-A-B, B-A-B-A-B-A-B, and higher oligomers. The ratio obtained from the area ratio of GPC was as follows.
B-A-B: 78%
B-A-B-A-B: 17%
B-A-B-A-B-A-B: 3%
More oligomers, etc .: 2%

The terminal isocyanate group content of Prepolymer 1 was 13.3 (wt%), and the resulting polymer was characterized using gel permeation chromatography. The molecular weight of the peak was 8900. There was one peak.

The analytical values of Prepolymer 1 were as follows.
(1) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.90 (m, 2H), 7.52 (m, 2H), 7.23 (m, 2H), 5.27 (m, 2H) ), 3.31 (m, 16H), 1.62 (m, 4H), 1.42 (m, 4H)
(2) IR (KBr, cm ⁻¹ ): 3240, 2930, 2890, 2280, 1710, 1540, 1480, 1380, 1260, 1220, 1160, 1120, 1060, 760

(Synthesis of Prepolymer 2)
4 g of commercially available styrene (Wako special grade) as a radical polymerizable compound was put in a test tube, and 1% by mass of azobisisobutyronitrile (Wako special grade) as a radical polymerization initiator for this radical polymerizable compound, a chain transfer agent. As a radical polymerizable composition, 5000 mass ppm of 1,4-naphthoquinone was added. The test tube containing the radical polymerizable composition was capped with a septum, and nitrogen was bubbled through the composition at a rate of 15 mL / min for 20 minutes. Then, the test tube is immersed in a heated oil bath while nitrogen is passed, and the solution temperature in the test tube is kept at 60 ° C. for 5 hours. The resulting solution is reprecipitated with a large amount of methanol and vacuumed. Drying gave about 0.2 g of polymer.

Furthermore, when the prepolymer 2 was characterized using gel permeation chromatography, the peak top molecular weight was 5400. There was one peak.

(Synthesis of block polymer)
Gel permeation is obtained by dissolving 0.1 g of prepolymer 1 obtained by the above reaction and 0.1 g of prepolymer 2 in 1 g of dimethylformamide in a test tube and reacting at 90 ° C. for 5 hours in a nitrogen atmosphere. When the produced polymer was characterized by using chromatography, a polymer having a peak with a molecular weight of 24,000 was obtained. It is estimated that this molecular weight peak was obtained from the molecular weight distribution of an oligomer obtained by reacting two molecules of prepolymer 1 (diisocyanate ester oligomer) having a molecular weight peak of 8900 and prepolymer 2 having a molecular weight peak of 5400. Is done.

From the results of Example 25, the prepolymer 2 polymerized using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention reacts with the prepolymer 1 having isocyanate groups at both ends to form a block polymer. You can see that That is, the terminal of the prepolymer 2 polymerized using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention has a residue derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. And it can be said that the said residue reacted with isocyanate and formed the block polymer. From this, it can be said that the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is a useful compound for synthesizing a terminal functionalized polymer having a reactive group.

Claims (10)

A chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (1).

(In the formula (1), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent, and are saturated or unsaturated 6-membered The 6-membered ring formed by X and Y may be further substituted with an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom. ) The chain transfer having a condensed polycyclic aromatic skeleton according to claim 1, wherein in general formula (1), n is 4, R is a hydrogen atom, and X and Y are hydrogen atoms. Agent. 2. The condensed polycyclic aromatic skeleton according to claim 1, wherein, in the general formula (1), X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom. A chain transfer agent. In the general formula (1), n is 4, R is a hydrogen atom, X is a hydroxy group or a methyl group, and Y is a hydrogen atom. A chain transfer agent having a ring aromatic skeleton. In the general formula (1), n is 4, R is a hydrogen atom, X is a chlorine atom, and Y is a chlorine atom or an amino group. A chain transfer agent having a ring aromatic skeleton. A chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (2) or (3).

(In the formula (2), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, each R independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an aryloxy group or a halogen atom, Q represents a hydrogen atom, an alkyl group or a halogen atom.) The radically polymerizable composition containing the chain transfer agent which has the condensed polycyclic aromatic skeleton as described in any one of Claims 1 thru | or 6, and a radically polymerizable compound. The radical polymerizable composition according to claim 7, wherein the radical polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene. A polymer obtained by radical polymerization of the radically polymerizable composition according to claim 7 or 8, which is derived from a chain transfer agent having the condensed polycyclic aromatic skeleton at the end of the polymer or a part of the main chain. A polymer having a residue. A terminal of a polymer or a part of a main chain, wherein a radical polymerizable compound is radically polymerized in the presence of a chain transfer agent having a condensed polycyclic aromatic skeleton according to any one of claims 1 to 6. And a method for producing a polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton.