JP6020876B2 - Chain transfer agent having condensed polycyclic aromatic skeleton, polymer having condensed polycyclic aromatic skeleton, and method for producing polymer - Google Patents

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 and 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, alkyl as a chain transfer agent is used. A mercaptan 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, mercaptan chain transfer agents are used in order to obtain low molecular weight and sharp molecular weight distribution when polymerizing styrene monomers and acrylic monomers. (For example, refer to Patent Documents 9 and 10).

In addition, the chain transfer agent is known not only to adjust the molecular weight as described above, but also to give its own residue to the polymer terminal 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 11 and 12, Non-Patent Documents 4 and 5). ).

On the other hand, since an aromatic compound having a sulfonate group can be used as an esterification catalyst, examples in which aromatic sulfonic acids having a phenolic hydroxyl group are used as a water-soluble esterification catalyst and polymerization inhibitor are known ( For example, Patent Documents 13 and 14). Moreover, the example which uses a naphthohydroquinonesulfonic acid as a polymerization inhibitor is known (patent document 15). However, in these examples, the use and purpose of use are limited to the action of prohibiting polymerization and are not aimed at the chain transfer effect, and there is no suggestion that it has the chain transfer effect.

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 Japanese Patent Publication No.57-10850 JP 2010-222285 A Japanese Patent Laid-Open No. 6-9495 JP-A-6-16594 JP 2008-239599 A

By AGE Odian PRINCIPLES OF POLYMERIZATION (FOURTH Edition) (2004) 238 pages Takatsu Otsu, “Chemistry of Polymer Synthesis” (Chemical Doujin, 1979) p. 93 Edited by Mikiharu Konoike, “Radical Polymerization Handbook” (NTS, 2010), p. 47 Shima Tanaka, Haruo Nishida, and Takeshi Endo, Macromolecules 2009, 42, 293-298 Tetsuo Ogawa, Research on paints, No. 137, Oct, 2001, p. 11

In the prior art as described above, for example, conventionally used chain transfer agents such as mercaptans such as dodecyl mercaptan, halogenated hydrocarbons such as carbon tetrachloride, and alpha methyl styrene dimer have a bad odor or environment. In addition to the above-mentioned disadvantages, both are hydrophobic and unsuitable for aqueous solution polymerization of acrylic acid, acrylamide and the like. On the other hand, water-soluble lower alcohols such as isopropanol also have chain transfer ability, but the ability is small, and water-soluble mercaptoethanol also has chain transfer ability, but has the disadvantage of high odor and toxicity, There was no sex chain transfer agent.

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 also 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, the present invention is to provide a new type of water-soluble chain transfer agent which has no problem of odor and has a large 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, the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is water-soluble. It has an excellent chain transfer effect in spite of having a structure that is completely different from conventionally known chain transfer agents, and has no atoms that adversely affect the environment such as halogen in the molecule. The inventors have found that a polymer having a condensed polycyclic aromatic skeleton derived from the chain transfer agent of the present invention can be produced, and 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 above general formula (1), n represents an integer of 1 or 2, m represents an integer of 6 or 7, and the sum of m and n is 8, and a plurality of Rs are the same as each other. Each represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and adjacent Rs are bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring. X may represent a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).

(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.)

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

(In the general formula (3), n represents an integer of 1 or 2, m represents an integer of 4 to 6, p represents an integer of 1 or 2, and the total of m, n, and p is 8) A plurality of Rs may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs are bonded to each other in place of the substituent and are saturated or unsaturated. A saturated 6-membered ring may be formed, and X represents a hydrogen atom, an alkali metal or ammonium represented by the following general formula (2).

(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.)

The third invention resides in a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (4).

(In the above general formula (4), n represents an integer of 1 or 2, m represents an integer of 4 or 5, and the sum of m and n is 6, and a plurality of Rs are the same as each other. Each may represent a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs may be bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring, X represents any one of a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).)

(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.)

The fourth invention resides in a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (5).

(In the general formula (5), X represents a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).)

(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.)

The fifth invention resides in a radically polymerizable composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton and a radically polymerizable compound as described in any one of the first to fourth inventions. .

A sixth invention resides in the radical polymerizable composition according to the fifth invention, wherein the radical polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene.

A seventh invention is a polymer obtained by radical polymerization of the radically polymerizable composition according to the fifth invention or the sixth invention, wherein the condensed polycyclic ring is formed at the end 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.

An eighth invention is characterized in that radical polymerization of a radically polymerizable compound in the presence of a chain transfer agent having a condensed polycyclic aromatic skeleton as described in any one of the first to fourth inventions, The present invention resides in a method for producing a polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton at the end of the polymer or part of the main chain.

In the present invention, (meth) acryl represents acryl or methacryl, and (meth) acrylamide represents acrylamide or methacrylamide.

The chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention has no unpleasant odor, is water-soluble, and can be used for a radical polymerizable compound to effectively adjust the molecular weight of a desired polymer. Further, the generation of unpleasant odor in the produced polymer can be suppressed. Furthermore, by polymerizing a radical polymerizable compound using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, a polymer having a condensed polycyclic aromatic skeleton at the terminal can be synthesized.

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

(In the above general formula (1), n represents an integer of 1 or 2, m represents an integer of 6 or 7, and the sum of m and n is 8, and a plurality of Rs are the same as each other. Each represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and adjacent Rs are bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring. X may represent a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).

(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.)

In the general formula (1), when one or two of R are hydroxy groups, the compound of the general formula (3) is obtained.

(In the general formula (3), n represents an integer of 1 or 2, m represents an integer of 4 to 6, p represents an integer of 1 or 2, and the total of m, n, and p is 8) A plurality of Rs may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs are bonded to each other in place of the substituent and are saturated or unsaturated. A saturated 6-membered ring may be formed, and X represents a hydrogen atom, an alkali metal, or ammonium represented by the general formula (2).

In the general formula (3), there are two hydroxy groups, and those having 1- and 4-positions of the naphthalene skeleton are compounds of the general formula (4).

(In the above general formula (4), n represents an integer of 1 or 2, m represents an integer of 4 or 5, and the sum of m and n is 6, and a plurality of Rs are the same as each other. Each may represent a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs may be bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring, X represents any one of a hydrogen atom, an alkali metal, or ammonium represented by the general formula (2).)

In the general formula (4), n is 1, the SO ₃ X group is located at the 2-position of the naphthalene skeleton, and all Rs are hydrogen atoms to form the compound of the general formula (5).

(In the general formula (5), X represents a hydrogen atom, an alkali metal, or ammonium represented by the general formula (2).)

In the general formulas (1) to (4), examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and tert-butyl. Group, an n-pentyl group, an n-hexyl group, a 2-ethylhexyl group, an n-decyl group, an n-dodecyl group and the like, and an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. And examples of the alkoxy group include alkoxy groups having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group.

In the general formulas (1) to (4), as examples in which adjacent Rs are bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring, two adjacent Rs are CH ₂ A CH ₂ group in which two adjacent R's are bonded by a single bond, two adjacent R's are CH ₂ CH groups, and two adjacent R's are bonded by a double bond, Two adjacent Rs are CH = CH groups, and two adjacent Rs are bonded by a single bond to form an aromatic ring. The 6-membered ring formed by two adjacent Rs may be further substituted with an alkyl group, a hydroxy group, an alkoxy group, or a sulfonyl group. 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, and a tert-butyl group. Group, ethoxy group, n-propoxy group, i-propoxy group and the like.

In the general formula (2), examples of the alkyl group represented by R ¹ , R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, Examples thereof include alkyl groups having 1 to 12 carbon atoms such as a tert-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group and n-dodecyl group, preferably 1 to 4 carbon atoms. Examples of the hydroxylalkyl group include a hydroxylethyl group and a hydroxylpropyl group.

Next, specific examples of the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention are shown. In the general formula (1), n is 1 or 2, two of R are hydroxy groups, and the compounds in the 1 and 4 positions of the naphthalene skeleton are the compounds of the general formula (4). First, the compound of the general formula (4) will be described.

In the general formula (4), a compound in which n is 1 and the SO ₃ X group is located at the 2-position of the naphthalene skeleton, and all R are hydrogen atoms is a compound of the general formula (5) Specific examples thereof include 1,4-dihydroxynaphthalene-2-sulfonic acid, sodium 1,4-dihydroxynaphthalene-2-sulfonate, potassium 1,4-dihydroxynaphthalene-2-sulfonate, 1,4-dihydroxynaphthalene-2-sulfonate, Examples thereof include ammonium dihydroxynaphthalene-2-sulfonate and triethylammonium salt of 1,4-dihydroxynaphthalene-2-sulfonic acid.

Next, specific examples of the compound represented by the general formula (4) other than the compound represented by the general formula (5) include 1,4-dihydroxynaphthalene-6-sulfonic acid, 1,4-dihydroxynaphthalene- Sodium 6-sulfonate, potassium 1,4-dihydroxynaphthalene-6-sulfonate, ammonium 1,4-dihydroxynaphthalene-6-sulfonate, triethylammonium salt of 1,4-dihydroxynaphthalene-6-sulfonic acid, 1, 4-dihydroxynaphthalene-2,3-disulfonic acid, sodium 1,4-dihydroxynaphthalene-2,3-disulfonate, potassium 1,4-dihydroxynaphthalene-2,3-disulfonate, 1,4-dihydroxynaphthalene-2 , 3-Disulfonic acid ammonium, 1,4-dihydroxynaphthalene-2,3 Triethylammonium salt of disulfonic acid, 1,4-dihydroxynaphthalene-2,6-disulfonic acid, sodium 1,4-dihydroxynaphthalene-2,6-disulfonic acid, potassium 1,4-dihydroxynaphthalene-2,6-disulfonic acid 1,4-dihydroxynaphthalene-2,6-disulfonic acid ammonium, 1,4-dihydroxynaphthalene-2,6-disulfonic acid triethylammonium salt, 1,4-dihydroxynaphthalene-5,7-disulfonic acid, Sodium 4-dihydroxynaphthalene-5,7-disulfonate, potassium 1,4-dihydroxynaphthalene-5,7-disulfonate, ammonium 1,4-dihydroxynaphthalene-5,7-disulfonate, 1,4-dihydroxynaphthalene- 5,7-Disulfonic acid Triethylammonium salt, 6-methyl-1,4-dihydroxynaphthalene-2-sulfonic acid, sodium 6-methyl-1,4-dihydroxynaphthalene-2-sulfonate, 6-methyl-1,4-dihydroxynaphthalene-2- Examples include potassium sulfonate, ammonium 6-methyl-1,4-dihydroxynaphthalene-2-sulfonate, and triethylammonium salt of 6-methyl-1,4-dihydroxynaphthalene-2-sulfonic acid.

Furthermore, as an example in which adjacent Rs are bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring, 9,10-dihydroxyanthracene-1-sulfonic acid, 9,10- Sodium dihydroxyanthracene-1-sulfonate, potassium 9,10-dihydroxyanthracene-1-sulfonate, ammonium 9,10-dihydroxyanthracene-1-sulfonate, triethylammonium salt of 9,10-dihydroxyanthracene-1-sulfonate 9,10-dihydroxyanthracene-2-sulfonic acid, sodium 9,10-dihydroxyanthracene-2-sulfonate, potassium 9,10-dihydroxyanthracene-2-sulfonate, 9,10-dihydroxyanthracene-2-sulfonic acid Ammonium, 9,10- Triethylammonium salt of hydroxyanthracene-2-sulfonic acid, 9,10-dihydroxyanthracene-2,6-disulfonic acid, 9,10-dihydroxyanthracene-2,6-disulfonic acid sodium salt, 9,10-dihydroxyanthracene-2, 6-disulfonic acid potassium, 9,10-dihydroxyanthracene-2,6-disulfonic acid ammonium, 9,10-dihydroxyanthracene-2,6-trisulfonic acid triethylammonium salt, 9,10-dihydroxyanthracene-2,7- Disulfonic acid, sodium 9,10-dihydroxyanthracene-2,7-disulfonic acid, potassium 9,10-dihydroxyanthracene-2,7-disulfonic acid, 9,10-dihydroxyanthracene-2,7-disulfonic acid Bromide, triethylammonium salt of 9,10-dihydroxy anthracene-2,7-disulfonic acid.

Specific examples of the compound represented by the general formula (3) other than the compounds represented by the general formulas (4) and (5) include 1-hydroxynaphthalene-2-sulfonic acid and 1-hydroxynaphthalene-2. Sodium sulfonate, potassium 1-hydroxynaphthalene-2-sulfonate, ammonium 1-hydroxynaphthalene-2-sulfonate, triethylammonium salt of 1-hydroxynaphthalene-2-sulfonic acid, 2-hydroxynaphthalene-1-sulfonic acid Sodium 2-hydroxynaphthalene-1-sulfonate, potassium 2-hydroxynaphthalene-1-sulfonate, ammonium 2-hydroxynaphthalene-1-sulfonate, triethylammonium salt of 2-hydroxynaphthalene-1-sulfonic acid, 1- Hydroxynaphthalene-4-sulfone 1-hydroxynaphthalene-4-sulfonic acid sodium salt, 1-hydroxynaphthalene-4-sulfonic acid potassium salt, 1-hydroxynaphthalene-4-sulfonic acid ammonium salt, 1-hydroxynaphthalene-4-sulfonic acid triethylammonium salt, Hydroxynaphthalene-5-sulfonic acid, sodium 1-hydroxynaphthalene-5-sulfonate, potassium 1-hydroxynaphthalene-5-sulfonate, ammonium 1-hydroxynaphthalene-5-sulfonate, 1-hydroxynaphthalene-5-sulfonic acid Triethylammonium salt of 2-hydroxynaphthalene-5-sulfonic acid, sodium 2-hydroxynaphthalene-5-sulfonate, potassium 2-hydroxynaphthalene-5-sulfonate, 2-hydroxynaphthalene-5 Ammonium sulfonate, triethylammonium salt of 2-hydroxynaphthalene-5-sulfonic acid, 2-hydroxynaphthalene-6-sulfonic acid, sodium 2-hydroxynaphthalene-6-sulfonate, potassium 2-hydroxynaphthalene-6-sulfonate, 2-hydroxynaphthalene-6-sulfonic acid ammonium, 2-hydroxynaphthalene-6-sulfonic acid triethylammonium salt, 1,2-dihydroxynaphthalene-4-sulfonic acid, 1,2-dihydroxynaphthalene-4-sulfonic acid sodium, 1,2-dihydroxynaphthalene-4-sulfonic acid potassium, 1,2-dihydroxynaphthalene-4-sulfonic acid ammonium, 1,2-dihydroxynaphthalene-4-sulfonic acid triethylammonium salt, 1,6-dihydro Droxynaphthalene-3-sulfonic acid, sodium 1,6-dihydroxynaphthalene-3-sulfonate, potassium 1,6-dihydroxynaphthalene-3-sulfonate, ammonium 1,6-dihydroxynaphthalene-3-sulfonate, 1, Triethylammonium salt of 6-dihydroxynaphthalene-3-sulfonic acid, 1,7-dihydroxynaphthalene-3-sulfonic acid, sodium 1,7-dihydroxynaphthalene-3-sulfonate, 1,7-dihydroxynaphthalene-3-sulfonic acid Potassium, ammonium 1,7-dihydroxynaphthalene-3-sulfonate, triethylammonium salt of 1,7-dihydroxynaphthalene-3-sulfonic acid, 1,8-dihydroxynaphthalene-4-sulfonic acid, 1,8-dihydroxynaphthalene- 4-s Sodium fonate, potassium 1,8-dihydroxynaphthalene-4-sulfonate, ammonium 1,8-dihydroxynaphthalene-4-sulfonate, triethylammonium salt of 1,8-dihydroxynaphthalene-4-sulfonic acid, 6,7- Dihydroxynaphthalene-2-sulfonic acid, sodium 6,7-dihydroxynaphthalene-2-sulfonate, potassium 6,7-dihydroxynaphthalene-2-sulfonate, ammonium 6,7-dihydroxynaphthalene-2-sulfonate, 6,7 -Triethylammonium salt of dihydroxynaphthalene-2-sulfonic acid, 1,3-dihydroxynaphthalene-5,7-disulfonic acid, sodium 1,3-dihydroxynaphthalene-5,7-disulfonate, 1,3-dihydroxynaphthalene-5 , 7-G Potassium sulfonate, ammonium 1,3-dihydroxynaphthalene-5,7-disulfonate, triethylammonium salt of 1,3-dihydroxynaphthalene-5,7-disulfonic acid, 1,2-dihydroxynaphthalene-3,6-disulfonic acid 1,2-dihydroxynaphthalene-3,6-disulfonic acid sodium salt, 1,2-dihydroxynaphthalene-3,6-disulfonic acid potassium salt, 1,2-dihydroxynaphthalene-3,6-disulfonic acid ammonium salt, 1,2- Triethylammonium salt of dihydroxynaphthalene-3,6-disulfonic acid, 1,5-dihydroxynaphthalene-2,4-disulfonic acid, sodium 1,5-dihydroxynaphthalene-2,4-disulfonate, 1,5-dihydroxynaphthalene- Potassium 2,4-disulfonate 1,5-dihydroxynaphthalene-2,4-disulfonic acid ammonium, 1,5-dihydroxynaphthalene-2,4-disulfonic acid triethylammonium salt, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, , 8-dihydroxynaphthalene-3,6-disulfonic acid sodium salt, 1,8-dihydroxynaphthalene-3,6-disulfonic acid potassium salt, 1,8-dihydroxynaphthalene-3,6-disulfonic acid ammonium salt, 1,8-dihydroxynaphthalene -Triethylammonium salt of 3,6-disulfonic acid, 2,7-dihydroxynaphthalene-3,6-disulfonic acid, sodium 2,7-dihydroxynaphthalene-3,6-disulfonic acid, 2,7-dihydroxynaphthalene-3, Potassium 6-disulfonate, 2,7-di Mud carboxymethyl-3,6-ammonium disulfonic acid, triethylammonium salt of 2,7-dihydroxy-3,6-disulfonic acid.

Furthermore, specific examples of the compound represented by the general formula (1) other than the compounds represented by the general formulas (3), (4) and (5) include naphthalene-1-sulfonic acid and naphthalene-1-sulfonic acid. Sodium, potassium naphthalene-1-sulfonate, ammonium naphthalene-1-sulfonate, triethylammonium salt of naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, sodium naphthalene-2-sulfonate, naphthalene-2-sulfonic acid Potassium, ammonium naphthalene-2-sulfonate, triethylammonium salt of naphthalene-2-sulfonic acid, naphthalene-2,6-disulfonic acid, sodium naphthalene-2,6-disulfonate, potassium naphthalene-2,6-disulfonate, Naphthalene-2,6-ammonium disulfonate, naphth Triethylammonium salt of len-2,6-disulfonic acid, 4-butylnaphthalene-1-sulfonic acid, sodium 4-butylnaphthalene-1-sulfonate, potassium 4-butylnaphthalene-1-sulfonate, 4-butylnaphthalene- 1-sulfonic acid ammonium, 4-butylnaphthalene-1-sulfonic acid triethylammonium salt, 2,6-dibutylnaphthalene-1-sulfonic acid, 2,6-dibutylnaphthalene-1-sulfonic acid sodium salt, 2,6-dibutyl Potassium naphthalene-1-sulfonate, ammonium 2,6-dibutylnaphthalene-1-sulfonate, triethylammonium salt of 2,6-dibutylnaphthalene-1-sulfonic acid, 2,6-dinonylnaphthalene-1-sulfonic acid, 2,6-Dinonylnaphthalene-1-sulfonic acid naphthalate Examples thereof include potassium, potassium 2,6-dinonylnaphthalene-1-sulfonate, ammonium 2,6-dinonylnaphthalene-1-sulfonate, and triethylammonium salt of 2,6-dinonylnaphthalene-1-sulfonic acid. .

Among these exemplified compounds, sodium 1-hydroxynaphthalene-4-sulfonate, potassium 1-hydroxynaphthalene-4-sulfonate, ammonium 1-hydroxynaphthalene-4-sulfonate, and 1-hydroxynaphthalene-4-sulfonic acid. Triethylammonium salt, sodium 2-hydroxynaphthalene-6-sulfonate, potassium 2-hydroxynaphthalene-6-sulfonate, ammonium 2-hydroxynaphthalene-6-sulfonate, triethylammonium salt of 2-hydroxynaphthalene-6-sulfonic acid 1,4-dihydroxynaphthalene-2-sulfonic acid sodium salt, 1,4-dihydroxynaphthalene-2-sulfonic acid potassium salt, 1,4-dihydroxynaphthalene-2-sulfonic acid ammonium salt, 1,4-dihydride Triethylammonium salt of xinaphthalene-2-sulfonic acid, sodium 1,6-dihydroxynaphthalene-3-sulfonate, potassium 1,6-dihydroxynaphthalene-3-sulfonate, ammonium 1,6-dihydroxynaphthalene-3-sulfonate 1,6-dihydroxynaphthalene-3-sulfonic acid triethylammonium salt, sodium 6,7-dihydroxynaphthalene-2-sulfonate, potassium 6,7-dihydroxynaphthalene-2-sulfonate, 6,7-dihydroxynaphthalene- A compound having an OH group in its skeleton, such as ammonium 2-sulfonate and triethylammonium salt of 6,7-dihydroxynaphthalene-2-sulfonic acid, is preferable in terms of high chain transfer ability, and in particular, 1,4-dihydroxynaphthalene. -2 Sodium sulfonate, potassium 1,4-dihydroxynaphthalene-2-sulfonate, ammonium 1,4-dihydroxynaphthalene-2-sulfonate, triethylammonium salt of 1,4-dihydroxynaphthalene-2-sulfonic acid have chain transfer ability Is particularly high and is preferable in that it is easy to synthesize.

Since the compound which is a hydrogen atom as X in General formula (1) shows strong acidity, when the polymeric compound etc. to add are acidic and unstable, it is necessary to use a neutralizing agent etc. together. On the other hand, if X is an alkali metal or ammonium, such as solubility in the solvent of the compound is different, since the general formula SO ₃ X group in (1), is dissociated strongly in solution, SO ₃ group and salts Regardless of the type of base such as alkali metal or ammonium that forms the base, there is no difference in the effect as a chain transfer agent because the existence probability of the base in the vicinity of the site of chain transfer is low.

[Radical polymerization]
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.

As the polymerization method, various polymerization methods such as solution polymerization, emulsion polymerization and suspension polymerization can be employed. Since the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention has water solubility, it is suitable for adjusting the degree of polymerization of a radically polymerizable compound in aqueous solution polymerization, emulsion polymerization and suspension polymerization.

In the aqueous solution polymerization method, water is used as a solvent, for example, a water-soluble ethylenically unsaturated monomer such as acrylic acid or a sodium salt thereof is mixed and dissolved with a radical polymerization initiator, and the aqueous solution is heated to polymerize. 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, usually, water is used as a medium, and a hydrophobic monomer that is hardly soluble in water such as vinyl acetate, styrene, or methyl methacrylate and a radical polymerization initiator are mixed in the presence of a surfactant. Stir and polymerize in the 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 can also be 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 methyl methacrylate, and a radical polymerization initiator in water using a dispersion stabilizer, the mixture is stirred and suspended. Polymerize in the state. 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.

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 with a polymerizable compound from the beginning to prepare a radical polymerizable composition, a polymerization reaction Occasionally known methods such as batch addition to the reaction system, method of batch addition in each step or in several batches depending on the degree of polymerization, method of continuous addition at a set time, or combinations thereof 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 a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention by dissolving it in water or an appropriate organic solvent, or a chain transfer agent having a polymerizable compound and a condensed polycyclic aromatic skeleton of the present invention. The mixture may be adjusted and added.

The blending amount of the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is usually preferably 0.005 to 10% by weight based on the radical polymerizable compound from the viewpoint of sufficient chain transfer effect and economy. 0.01 to 5% by weight is more preferable.

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 (meth) acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic Α, β-unsaturated carboxylic acid ester compounds such as octyl acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate; vinyl ester compounds such as vinyl acetate; acrylamide, methacryl Acrylamide compounds such as amide and N, N-dimethylacrylamide; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and divinylbenzene; substituted ethylene compounds such as acrylonitrile, vinyl chloride, and vinylidene chloride; ethylene, propylene Examples include ethylenically unsaturated compounds such as butene, butadiene, isoprene, cyclopentadiene, and pinene, and unsaturated organic silane compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and vinyltrimethoxysilane. It is done.

Among the radical polymerizable compounds, α, β-unsaturated carboxylic acid compounds, α, β-unsaturated carboxylic acid ester compounds, aromatic vinyl compounds, acrylamide compounds, and vinyl ester compounds are preferable.

Among these compounds, (meth) acrylic acid which is an α, β-unsaturated carboxylic acid compound, (meth) acrylic acid ester which is an α, β-unsaturated carboxylic acid ester, and styrene which is an aromatic vinyl compound are preferable. .

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, benzoyl peroxide, di-t-amyl peroxide, t-butyl peroxybenzoate, 2,5-dimethyl-2,5 di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Di- (t-butylperoxy) hexyne-3, and peroxides such as di-cumyl peroxide, hydroperoxides such as t-amyl hydroperoxide, t-butyl hydroperoxide, and hydrogen peroxide, (2,2′-azobis (2,4-dimethylpentanenitrile)), (2,2′-azobis (2-methylpropanenitrile)), (2,2′-azobis (2-methylbutanenitrile)), (2,2′-azobis) (Cyclohexanecarbonitrile)) and the like.

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.

[Radically polymerizable composition]
The chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention can also 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.

[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.

Since the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention has water solubility, the condensed polycyclic ring is formed at the terminal of the polymer or a part of the main chain by aqueous solution polymerization, emulsion polymerization or suspension polymerization. It is suitable for producing a polymer having a residue derived from a chain transfer agent having an aromatic skeleton.

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. In addition, since the chain transfer agent having a condensed polycyclic aromatic skeleton of the invention has water solubility, it becomes possible to hydrophilize the polymer terminal, improve compatibility with other compounds and familiarity, It becomes possible to adjust the hydrophilic / lipophilic balance. In addition, those that are particularly reactive can be used as raw materials for block polymers, graft polymers, and macromonomers.

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
Commercially available acrylic acid containing 200 ppm by weight of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd., special grade) as a polymerization inhibitor was carried out 3 times to remove p-methoxyphenol. 2 g of this acrylic acid, 4 g of 1,4-dioxane as a hydrophilic solvent are put in a test tube, 0.02 g of azobisisobutyronitrile (made by Wako Pure Chemical Industries, special grade) as an initiator, and 30 as a chain transfer agent. 0.003 g of a weight% aqueous solution of ammonium 1,4-naphthoquinone-2-sulfonate (hereinafter abbreviated as NHQS (NH 4)) was added to make a radical 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 nitrogen was passed, and the solution temperature in the test tube was kept at 60 ° C. for 2 hours. The product is treated with bistrimethylsilylacetamide and dissolved in tetrahydrofuran (made by Wako Pure Chemical Industries, special grade) at a predetermined concentration. The produced polymer was characterized using a gel permeation chromatography (manufactured by JASCO Corporation) equipped with a meter (manufactured by JASCO Corporation MD-2010) and a GPC column (Showa Denko Shodex GPC KF-806L). Of these, a refractometer was used as a detector, and the average molecular weight of the produced polymer and its distribution were measured. 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.

(Example 2)
The same operation as in Example 1 was performed except that the addition amount of 30 wt% NHQS (NH 4) aqueous solution as a chain transfer agent was changed from 0.003 g to 0.03 g, and measurement results such as the average molecular weight of the obtained polymer were obtained. It is shown in Table 1.

(Comparative Example 1)
The same operation as in Example 1 was performed except that a 30 wt% NHQS (NH 4) aqueous solution was not added as a chain transfer agent, and the measurement results are shown in Table 1.

From the comparison between Examples 1 and 2 and Comparative Example 1, the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention has a wide molecular weight ranging from an oligomer having a molecular weight of less than 10,000 to a high polymer having a molecular weight of more than 10,000 with a small addition. It can be seen that it has excellent chain transfer ability that can be controlled.

Further, in the ultraviolet absorption spectrum of the produced polymer, absorption at a wavelength of 350 to 500 nm is not observed in Comparative Example 1, whereas Example 1 using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention is used. 2 is observed, when the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention is used, it is derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention in the produced polymer. It can be seen that a condensed polycyclic aromatic skeleton is introduced.

Claims (5)

A radical polymerizable composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (3), a radical polymerization initiator, and a radical polymerizable compound.
(In the general formula (3), n represents an integer of 1 or 2, m represents an integer of 4 to 6, p represents an integer of 1 or 2, and the total of m, n, and p is 8) A plurality of Rs may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs are bonded to each other in place of the substituent and are saturated or unsaturated. A saturated 6-membered ring may be formed, and X represents a hydrogen atom, an alkali metal or ammonium represented by the following general formula (2).
(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.) A radical polymerizable composition comprising a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (4), a radical polymerization initiator, and a radical polymerizable compound.
(In the above general formula (4), n represents an integer of 1 or 2, m represents an integer of 4 or 5, and the sum of m and n is 6, and a plurality of Rs are the same as each other. Each may represent a hydrogen atom, an alkyl group or an alkoxy group, and adjacent Rs may be bonded to each other instead of the substituent to form a saturated or unsaturated 6-membered ring, X represents any one of a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).)
(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.) A radical polymerizable composition comprising a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (5), a radical polymerization initiator, and a radical polymerizable compound.
(In the general formula (5), X represents a hydrogen atom, an alkali metal, or ammonium represented by the following general formula (2).)
(In the above general formula (2), R ¹ , R ² and R ³ may be the same or different from each other, and each represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. * Represents a bond. Show.) The radically polymerizable composition according to any one of claims 1 to 3, wherein the radically polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene. A radically polymerizable composition according to any one of claims 1 to 4 is subjected to radical polymerization by applying thermal energy or ionizing wave energy to a polymer end or a part of a main chain, A method for producing a polymer having a residue derived from a chain transfer agent having a ring aromatic skeleton.