JP2001026610A - Preparation of polymer and polymerization mediator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform polymer in which polymerization proceeds at relatively low temperatures in a living manner and which has a high molecular weight but a small polydispersity by radical polymerizing a radical-polymerizable monomer in the presence of an N-oxyl compound or its ether derivative or acyl derivative. SOLUTION: An N-oxyl compound of the formula or its ether derivative or acyl derivative is used. In the formula, R1 and R2 together form an oxo, or R1 is H, an hydroxy group or an amino group and R2 is H; and -A- and -B- each is a three to seven-membered cycloalkyl group containing the carbon atoms it is linked to. A styrene-based monomer, especially styrene is suitable as the radical-polymerizable monomer. An organic peroxide compound or an azo-based compound, especially benzoyl peroxide is suitable as the radical polymerization initiator. The temperature at which polymerization is initiated is usually 70-160 deg.C, and the temperature at which polymerization proceeds in a living manner is preferably 100 deg.C or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radical-polymerizable monomer, which is optionally substituted with a 4-substituent at the 4-position represented by the formula (I). The present invention relates to a polymer production method characterized by radical polymerization in the presence of an alkylpiperidine-N-oxyl compound, an ether derivative or an acyl derivative thereof, and an N-oxyl compound or a derivative thereof that functions as a mediator in the method.

[0002]

A stable nitroxide radical such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) (also referred to as nitroxyl)
When styrene is used as a mediator to radically polymerize styrene at 110 ° C. or higher, the molecular weight increases linearly with the polymerization rate, and the polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the obtained polymer is 1.3 or less, indicating that polymerization proceeds in a living manner (MK Georges et al., Macromolecule, 1993, 26
Volume, pp. 2987-2988, RD Puts et al., Macromolecule, 1996
Year, Vol. 29, pp. 3323-3325). However, if the polymerization is 110 degrees Celsius
If the reaction is carried out at a high reaction temperature, the polymerization initiated by thermal initiation competes as a side reaction and the degree of dispersion increases, making it difficult to obtain a uniform polymer. Since energy is required, it also increases the production cost of the polymer. Further, it has been confirmed that a radical polymerization reaction of styrene proceeds in a living manner at 80 degrees Celsius using di-t-butyl nitroxide as a mediator, but only a polymer having a low conversion is obtained (SO Hammouuch). Other, Macromol. Rap
id Commun., 1993, 26, 2987-2988).

The present inventors have developed an N-oxyl compound such as 2,6-dispiro-1 ', 1 "-dicycloalkylpiperidine-N-oxyl which may have a substituent at the 4-position as a mediator. When used, the radical polymerization of the olefinic monomer proceeds in a living manner at a relatively low temperature (most preferably in the temperature range of 70 to 90 degrees Celsius), and a uniform polymer having a molecular weight of 100,000 or more is obtained. Heading, the present invention has been completed.

In the present invention, among the N-oxyl compounds which function as mediators of the radical polymerization reaction, 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-oxopiperidine-N-oxyl is a compound known in the literature. However, only the use of the polymer as a light stabilizer is known (T. Yoshida et al., Bull. Chem. Soc.
Jpn., 1972, 45 (2), 636-638).

[0005]

According to the present invention, (1) a radically polymerizable monomer is represented by the general formula (I):

[0006]

Embedded image (Wherein R ¹ and R ² together represent an oxo group, or R ¹ is a hydrogen atom, a hydroxyl group or an amino group,
R ² represents a hydrogen atom; the groups represented by -A- and -B- are the same or different and together with the carbon atom to which they are attached, represent a 3- to 7-membered cycloalkyl group. (2) A method for producing a polymer, characterized in that radical polymerization is carried out in the presence of an N-oxyl compound represented by the formula (1) or an ether derivative or an acyl derivative thereof. The method for producing a polymer according to (3) or (2), wherein the radical polymerization initiator is a peroxide or an azo compound. The method for producing a polymer according to (4) or (2), Is a benzoyl peroxide (BPO) or an azobisisobutyronitrile (AIBN), (5) The monomer according to any one of (1) to (4), wherein Is a styrene-based monomer, an acrylic-based monomer or a methacryl-based monomer, (6) (1) In any one of Itaru (4),
(7) The method for producing a polymer according to any one of (1) to (6), wherein the radically polymerizable monomer is a styrene-based monomer. A method for producing a polymer, wherein the groups represented by A- and -B- are, together with the carbon atom to which they are attached, a cyclohexyl group;
(8) In any one of (1) to (7), R ¹ and R of the N-oxyl compound represented by the formula (I)
^2, or an oxo group together, or R ¹ is a hydroxyl group, a polymer production method, wherein R ² is a hydrogen atom, any one of (9) (1) to (8) , Wherein radical polymerization is started at 100 to 140 degrees Celsius, (10) and (1).
Any one of the above (8) to (8), wherein the radical polymerization is carried out at a reaction temperature of 70 to 100 ° C., (11) a general formula (I)

[0007]

Embedded image A radical polymerization reaction mediator containing an N-oxyl compound represented by the formula (I) or an ether derivative or an acyl derivative thereof as an active ingredient; (12) a general formula (I)

[0008]

Embedded image (However, excluding 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-oxopiperidine-N-oxyl), its ether derivative or acyl derivative.

In the above, the term "monomer capable of radical polymerization" refers to a monomer capable of forming a polymer by chain-linking by a radical reaction. As the “radical polymerizable monomer”, for example, styrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, methoxystyrene, 3,5-diethylstyrene, 4-n-propylstyrene, 2,4,6 -Trimethylstyrene, 4-
Phenylstyrene, 4-p-tolylstyrene, 3,5-
Styrene-based monomers such as diphenylstyrene, 1-vinylnaphthalene, 3-ethyl-1-vinylnaphthalene, 3-phenyl-1-vinylnaphthalene, pN, N-dimethylaminostyrene, sodium styrenesulfonate; acrylic acid; Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, se acrylate
Acrylic monomers such as c-butyl, t-butyl acrylate, pentenyl acrylate, heptenyl acrylate, allyl acrylate, glycidyl acrylate, acrylamide, acrylonitrile; methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl acrylate, isopropyl methacrylate, butyl methacrylate,
Isobutyl methacrylate, sec-butyl methacrylate,
Examples include methacrylic monomers such as t-butyl methacrylate, pentenyl methacrylate, heptenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylamide, and methacrylonitrile; and butadiene monomers such as butadiene. Preferred monomers among these are styrenic monomers,
Particularly preferred is styrene. In addition, these monomers can be used alone or in combination of two or more.

The "radical polymerization initiator" is a radical polymerization reaction initiator capable of initiating a free radical polymerization step to form a polymer compound. As the “radical polymerization initiator”, for example, benzoyl peroxide (B
Organic peroxides such as PO); azo compounds such as azobisisobutyronitrile (AIBN); and inorganic peroxides such as potassium persulfate / sodium bisulfite. Among these, preferred are organic peroxides and azo compounds, and particularly preferred is benzoyl peroxide (BPO).

A preferable combination of R ¹ and R ^{2 in} the N-oxyl compound (I) is that R ¹ and R ² are an oxo group together or R ¹ is a hydroxyl group and R ² is a hydrogen atom Is a combination.

The "3- to 7-membered cycloalkyl group" of the "group represented by -A- and -B-" includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. Preferred among them is a cyclohexyl group. -A- and-
The groups represented by B- may be the same or different, but are preferably the same.

Examples of the N-oxyl compound (I) include 2,6-dispiro-1 ', 1 "-dicyclopropylpiperidine-N-oxyl, 2,6-dispiro-1',
1 "-dicyclobutylpiperidine-N-oxyl, 2,
6-dispiro-1 ', 1 "-dicyclopentylpiperidine-N-oxyl, 2,6-distiro-1', 1" -dicyclohexylpiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-di Cycloheptylpiperidine-N
-Oxyl, 2,6-dispiro-1 ′, 1 ″ -dicyclopropyl-4-oxopiperidine-N-oxyl,
6-dispiro-1 ', 1 "-dicyclobutyl-4-oxopiperidine-N-oxyl, 2,6-dispiro-
1 ′, 1 ″ -dicyclopentyl-4-oxopiperidine-N-oxyl, 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-oxopiperidine-N-oxyl,
2,6-dispiro-1 ′, 1 ″ -dicycloheptyl-4
-Oxopiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicyclopropyl-4-hydroxypiperidine-N-oxyl, 2,6-dispiro-1', 1"
-Dicyclobutyl-4-hydroxypiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicyclopentyl-4-hydroxypiperidine-N-oxyl,
6-dispiro-1 ', 1 "-dicyclohexyl-4-hydroxypiperidine-N-oxyl, 2,6-dispiro-1', 1" -dicycloheptyl-4-hydroxypiperidine-N-oxyl, 2,6- Dispiro-1 ', 1 "
-Dicyclopropyl-4-aminopiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicyclobutyl-4-aminopiperidine-N-oxyl, 2,6-dispiro-1', 1" -dicyclo -4-aminopentylpiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "
-Dicyclohexyl-4-aminopiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicycloheptyl-4-aminopiperidine-N-oxyl, and the like. Of these, preferred are 2,6-dispiro-1 ′, 1 ″ -dicyclohexylpiperidine-N-
Oxyl, 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-oxopiperidine-N-oxyl, 2,6
-Dispiro-1 ', 1 "-dicyclohexyl-4-hydroxypiperidine-N-oxyl and 2,6-dispiro-1', 1" -dicyclohexyl-4-aminopiperidine-N-oxyl, more preferably 2 , 6-Dispiro-1 ', 1 "-dicyclohexyl-4-oxopiperidine-N-oxyl and 2,6-dispiro-1', 1"
-Dicyclohexyl-4-hydroxypiperidine-N-
Oxyl.

In the above N-oxyl compound (I),
When R ¹ is an amino group or a hydroxyl group, and R ² is a hydrogen atom, an “acyl derivative” in which the amino group and the hydroxyl group are modified with an acyl group can also be used as a mediator of living radical polymerization. Such acyl groups include, for example, formyl, acetyl, propionyl,
Butyryl, 4-hydroxybutyryl, valeryl, 5-hydroxyvaleryl, hexanoyl, 6-hydroxyhexanoyl, octanoyl, decanoyl, dodecanoyl,
An alkanoyl group having 1 to 18 carbon atoms which may be substituted by a hydroxyl group such as tetradecanoyl, hexadecanoyl and octadecanoyl; an arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl, tolyl and naphthoyl Can be mentioned. Of these, alkanoyl groups having 1 to 8 carbon atoms are preferred. Also, the formula HOOC (C
H ₂ ) n COOH (wherein n is an integer of 1 to 14), even when two molecules of the N-oxyl compound (I) are acylated by an aliphatic dicarboxylic acid having 3 to 16 carbon atoms. Often, a preferred n is between 4 and 10, and a most preferred n is 8.

In the N-oxyl compound (I), when R ¹ is a hydroxyl group and R ² is a hydrogen atom, an “ether derivative” in which the hydroxyl group is modified with an ether residue is also a mediator of living radical polymerization. Can be used as Examples of such an ether residue include an alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl. . Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable. Two molecules of the N-oxyl compound (I) are etherified with an aliphatic diol having 2 to 10 carbon atoms represented by the formula HO (CH ₂ ) mOH (wherein m is an integer of 2 to 10). The preferred n is from 3 to 6, and the most preferred m is 4.

Examples of the ether derivative or acyl derivative of the compound represented by the formula (I) include 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-methoxypiperidine-N-oxyl, 1 ', 1 "
-Dicyclohexyl-4-ethoxypiperidine-N-oxyl, 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-propoxypiperidine-N-oxyl, 2,
6-dispiro-1 ', 1 "-dicyclohexyl-4-butoxypiperidine-N-oxyl, butane-1,4-diolbis (2,6-dispiro-1', 1" -dicyclohexylpiperidine-N-oxyl-4- Yl) ether, hexane-1,6-diol bis (2,6-dispiro-1 ′, 1 ″ -dicyclohexylpiperidin-N-oxyl-4-yl) ether, octane-1,8-diolbis (2,6-dispiro) -1 ', 1 "-dicyclohexylpiperidin-N-oxyl-4-yl) ether, decane-1,10-diolbis (2,6-dispiro-1', 1" -dicyclohexylpiperidin-N-oxyl-4-yl ) Ether, 2,6-dispiro-
1 ', 1 "-dicyclohexyl-4-acetoxypiperidine-N-oxyl, 2,6-dispiro-1', 1"-
Dicyclohexyl-4-propionyloxypiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-butyryloxypiperidine-N-oxyl, 2,6-distiro-1', 1" -dicyclohexyl -4- (4-Hydroxybutyryl) oxypiperidine-N-oxyl, 2,6-dispiro-1 ', 1 "-dicyclohexyl-4- (6-hydroxyhexanoyl)
Oxypiperidine-N-oxyl, butane-1,4-diacid bis (2,6-dispiro-1 ′, 1 ″ -dicyclohexylpiperidin-N-oxyl-4-yl) ester,
Hexane-1,6-diacid bis (2,6-dispiro-
1 ′, 1 ″ -dicyclohexylpiperidin-N-oxyl-4-yl) ester, bis (2,6-dispiro-1 ′, 1 ″ -dicyclohexylpiperidine-N-oxyl-4-octane-1,8-dioate) Yl) ester, bis (2,6-dispiro-1 ′, 1 ″) decane-1,10-dioate
-Dicyclohexylpiperidin-N-oxyl-4-yl) ester and the like. Of these, 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-methoxypiperidine-N-oxyl, butane-1,4-diolbis (2,6-dispiro-1 ′,
1 "-dicyclohexylpiperidine-N-oxyl-4
-Yl) ether, 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-acetoxypiperidine-N-oxyl, 2,6-dispiro-1', 1" -dicyclohexyl-4-butyryloxypiperidine-N -Oxyl,
2,6-dispiro-1 ', 1 "-dicyclohexyl-4
-(6-hydroxyhexanoyl) oxypiperidine-
N-oxyl or decane-1,10-diacid bis (2,6
-Dispiro-1 ', 1 "-dicyclohexylpiperidin-N-oxyl-4-yl) ester.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A method for producing a polymer using a radical polymerization reaction using an N-oxyl compound (I) as a mediator according to the present invention will be described in detail.

As the reaction conditions to be used, polymerization conditions employed in ordinary radical polymerization reactions can be used. However, in order not to deactivate the polymerization initiator and the living site at the terminal of the polymer, oxygen is contained in the polymerization system. It is preferable to carry out the reaction under conditions that do not cause contamination. For example, a radically polymerizable monomer, a polymerization initiator, and an N-oxyl compound (I) or an acyl derivative thereof are mixed under a high vacuum or in an oxygen-free nitrogen or argon atmosphere, and then the decomposition temperature of the polymerization initiator is first determined. To complete decomposition of the polymerization initiator and then continue the polymerization reaction at an appropriate temperature at which radical polymerization proceeds in a living manner.

The present polymerization reaction can be carried out in the absence of a solvent, but can also be carried out in the presence of a suitable solvent. The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the raw materials to some extent.
For example, water; aromatic hydrocarbons such as benzene, toluene, and xylene; propane, n-butane, isobutane, n
Aliphatic hydrocarbons such as pentane, n-hexane, n-heptane, n-octane, isooctane, decane, hexadecane, isopentene and n-hexene; fats such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane Cyclic hydrocarbons; ethers such as tetrahydrofuran, dioxane, diethyl ether, dibutyl ether, ethylene glycol diethyl ether; methanol, ethanol, propanol,
Isopropanol, butanol, cyclohexanol,
Alcohols such as octanol and ethylene glycol can be mentioned. Preferably, it is an aromatic hydrocarbon such as benzene or toluene. In addition, these solvents can be used alone or in combination of two or more kinds at an arbitrary ratio.

The temperature at which the polymerization reaction is initiated and the time required for the initiation vary depending on the polymerization initiator used.
70 to 160 degrees Celsius for 5 minutes to 60 minutes, preferably 100 to 140 degrees Celsius for 10 to 30 minutes, and most preferably 120 degrees Celsius for 20 minutes.

The temperature at which the polymerization reaction proceeds in a living manner depends on the type of the monomer, N-oxyl compound and solvent used, but generally avoids competition with the radical polymerization reaction due to thermal decomposition and has a low polydispersity. In order to obtain a uniform polymer, it is preferable to carry out at a temperature of 100 degrees Celsius or less. Most preferably, it can be polymerized in a living manner at 70 to 100 degrees Celsius.

When a living radical polymerization reaction is carried out,
Depending on the type of the monomer, the N-oxyl compound and the solvent used, and the reaction temperature, the polymerization rate may be slow.Camphorsulfonic acid, sulfonic acid such as 2-fluoro-1-methylpyridinium p-toluenesulfonic acid or The polymerization reaction can be accelerated by adding a catalytic amount of the salt as an additive, and a polymer having a high conversion can be produced in a short time.

In the polymerization reaction of the present invention, a copolymer having an arbitrary monomer composition can be obtained by polymerizing two or more radically polymerizable monomers in combination. After the polymerization of one type of monomer is completed,
Subsequently, by sequentially polymerizing with another type of monomer, a block copolymer having an arbitrary monomer composition and structure (a diblock copolymer, a triblock copolymer, a multiblock copolymer, etc.) can be obtained. . Further, by adding a polyfunctional monomer such as divinylbenzene to the polymerization system during or at the end of the polymerization of the monomer, the polymer can have a branched structure or the molecular weight distribution can be expanded.

The molecular weight of the polymer obtained according to the present invention is almost uniquely determined by the molar ratio between the monomer and the polymerization initiator or the N-oxyl compound. By changing the ratio, the molecular weight of the polymer can be easily controlled over a wide range. The range of molecular weight that can be controlled is about 500 to 500,000 in number average molecular weight. Also, the polydispersity of the polymer obtained [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / M
n)] is usually in the range of 1.0 to 1.3. In the polymer production method of the present invention, the N-oxyl compound represented by the formula (I), which functions as a mediator of a radical polymerization reaction, and its ether derivative and acyl derivative can be produced by the following method.

[0025]

Embedded image In the above formula, -A-, -B-, R ¹ and R ² have the same meanings as described above. Hereinafter, each step will be described in detail.
All units in the description of reaction temperature are degrees Celsius (° C.). (Step A-1) Step A-1 is a step of reacting compound (II) with a 3- to 7-membered cycloalkanone in the presence of water and an ammonium salt to prepare a 2,6-dispiro-4-oxopiperidine compound ( III).

Compound (II) can be produced by the method of Reference Example 1 described later.

The 3- to 7-membered cycloalkanone is selected from cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone and cycloheptanone. When the -A- and -B- moieties are the same group, one type of cycloalkanone is selected, but -A- and -B-
If the moieties are different groups, two cycloalkanones are selected.

As the ammonium salt, for example, ammonium chloride, ammonium bromide, ammonium carbonate, ammonium acetate and the like can be used, but ammonium bromide is preferred.

The reaction temperature varies depending on the type of raw materials used, but is usually from 0 ° to 50 ° C., preferably from 10 ° C.
To 30 degrees.

The reaction time varies depending on the type of raw materials used and the reaction temperature, but is usually 1 to 72 hours, preferably 8 to 48 hours.

After completion of the reaction, the desired compound (III) can be isolated from the reaction solution by a commonly used method. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent.
Further, the obtained compound (III) is optionally subjected to distillation,
It can be purified by means such as recrystallization, reprecipitation and column chromatography. (Step A-2) In the step A-2, the carbonyl group at the 4-position of the piperidine ring of the compound (III) is chemically converted to give R
^This is a step of producing a compound (IV) in which ¹ is a hydrogen atom, a hydroxyl group or an amino group, and R ² is a hydrogen atom. (1) Production of compound (IVa) in which R ¹ is a hydroxyl group and R ² is a hydrogen atom Compound (IVa) in which R ¹ is a hydroxyl group and R ² is a hydrogen atom
a) can be produced by reacting compound (III) with a reducing agent in a solvent.

As the reducing agent, a reducing agent capable of converting a carbonyl group into an alcohol can be used, and examples thereof include metal hydrides such as sodium borohydride, lithium borohydride and lithium aluminum hydride. be able to. Preferably it is sodium borohydride or lithium aluminum hydride.

The reducing agent can be used usually in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, based on compound (III) as a raw material.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent.
Alcohols such as methanol and ethanol; ethers such as ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride And halogenated hydrocarbons such as chloroform. Among these, when the reducing agent is sodium borohydride, alcohols (particularly, ethanol) are preferable,
When the reducing agent is lithium aluminum hydride, ethers (particularly tetrahydrofuran) are preferred.

The reaction temperature varies depending on the type of the raw material and the reducing agent used, but is usually from -20 to 50 degrees, preferably from 0 to 30 degrees.

The reaction time varies depending on the starting materials used, the type of reducing agent and the reaction temperature, but is usually from 10 minutes to 24 hours, preferably from 1 to 4 hours.

After the completion of the reaction, the desired compound (IVa) can be isolated from the reaction solution by a commonly used method. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent.
Further, the obtained compound (IVa) is optionally subjected to distillation,
It can be purified by means such as recrystallization, reprecipitation and column chromatography. (2) R ¹ is an amino group, a manufacturing R ¹ is an amino group of R ² is a hydrogen atom (IVb), R ² is a hydrogen atom (I
Vb) can be produced by reacting compound (III) with a reducing agent in the presence of ammonia or an ammonium salt in a solvent.

As the reducing agent, a reducing agent capable of converting an imino group into an amino group can be used. For example, sodium borohydride, lithium borohydride, sodium cyanoborohydride, lithium aluminum hydride and the like can be used. Such metal hydrides can be mentioned. Preferably it is sodium borohydride or sodium cyanoborohydride.

The reducing agent can be used usually in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, based on compound (III) as a raw material.

As the ammonia or ammonium salt,
Those capable of converting a carbonyl group into an imino group can be used, and examples thereof include aqueous ammonia, ammonium chloride, ammonium bromide, ammonium carbonate, and ammonium acetate. Of these, ammonia water is preferred.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent.
Alcohols such as methanol and ethanol; ethers such as ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride And halogenated hydrocarbons such as chloroform. Of these, alcohols (particularly ethanol) are preferred.

The reaction temperature varies depending on the type of the starting material and the reducing agent used, but is usually from -20 to 50 degrees, preferably from 0 to 30 degrees.

The reaction time varies depending on the starting materials used, the reducing agent and the reaction temperature, but is usually from 10 minutes to 24 hours, preferably from 1 to 4 hours.

After the completion of the reaction, the desired compound (IVb) can be isolated from the reaction solution by a commonly used method. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent.
Further, the obtained compound (IVb) is optionally subjected to distillation,
It can be purified by means such as recrystallization, reprecipitation and column chromatography. (3) Compounds in which R ¹ and R ² are both hydrogen atoms (IV
Preparation of c) Compound (IVc) wherein R ¹ and R ² are both hydrogen atoms
Can be produced by reacting compound (III) with a reducing agent in a solvent.

As the reducing agent, a reducing agent capable of converting a carbonyl group to a methylene group can be used. For example, hydrazines such as hydrazine, carbamoylhydrazine, tosylhydrazine and potassium hydroxide,
Combinations of strong bases such as sodium ethoxide and potassium t-butoxide can be mentioned. Preferably, it is a combination of hydrazine and potassium hydroxide.

When a reducing agent in which a hydrazine and a strong base are combined is used, first, the hydrazine is allowed to act on the compound (III) in a solvent to form a hydrazone derivative of the compound (III). To convert to compound (IVc).

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent.
High boiling alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol are preferred.

The reaction temperature varies depending on the type of raw materials used, but is usually from 60 to 200 degrees, preferably from 100 to 150 degrees.

The reaction time varies depending on the starting materials used, the reducing agent and the reaction temperature, but is usually from 1 hour to 24 hours, preferably from 1 to 6 hours.

After the completion of the reaction, the desired compound (IVc) can be isolated from the reaction solution by a commonly used method. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent.
Further, the obtained compound (IVc) is optionally subjected to distillation,
It can be purified by means such as recrystallization, reprecipitation and column chromatography.

Of the compound (IV) thus obtained,
Compounds (IVa) and (IVb) in which R ¹ is an amino group or a hydroxyl group and R ² is a hydrogen atom can be prepared according to a known method, for example, the annual report of Sankyo Institute, 1983, Vol. 35, p. 1; Bull. Chem. S
oc. Jpn., 1997, 70, 275; Macromolecules, 199.
The method can be derived from the ether derivative or the acyl derivative by using the method described in Polymer Processing, 1998, vol. 47, p. 354, or the like, or a method analogous thereto.

For example, among the compounds (IV), acyl derivatives of the compounds (IVa) and (IVb) in which R ¹ is an amino group or a hydroxyl group and R ² is a hydrogen atom are the compounds (IVa) or (IVb) By reacting the activated acyl compound in a solvent in the presence of a base.

The activated acyl compounds include, for example, acyl halides such as carboxylic acid chloride, carboxylic acid bromide and sulfonic acid chloride; acyl acid anhydrides such as carboxylic acid anhydride; acyl imidazoles such as acetylimidazole And the like. Of these, carboxylic acid chloride (especially acetyl chloride) or carboxylic anhydride (especially acetic anhydride) is preferred. An activated product of an aliphatic dicarboxylic acid having 3 to 16 carbon atoms represented by the formula HOOC (CH ₂ ) n COOH (where n is an integer of 1 to 14) is also used.

Examples of the base to be used include trialkylamines such as triethylamine and diisopropylethylamine; aromatic amines such as pyridine; alkali metal hydroxides such as sodium hydroxide; sodium hydrogen carbonate and sodium carbonate. And preferred are trialkylamines (particularly triethylamine) and aromatic amines (particularly pyridine).

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent.
Ethers such as ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; esters such as ethyl acetate;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Of these, ethers (particularly tetrahydrofuran) or halogenated hydrocarbons (particularly methylene chloride) are preferred.

The reaction temperature varies depending on the types of the starting materials, the base and the acylating agent to be used.
Degrees, preferably between 0 and 30 degrees.

The reaction time varies depending on the starting materials used, the base, the type of acylating agent and the reaction temperature, but is usually from 10 minutes to 24 hours, preferably from 1 to 4 hours.

After completion of the reaction, the produced acyl derivative can be isolated from the reaction solution by a commonly used method. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent.
Further, the obtained acyl derivative can be purified by means of distillation, recrystallization, reprecipitation, column chromatography or the like, if necessary.

In the compound (IV), the ether derivative of the compound (IVa) in which R ¹ is a hydroxyl group and R ² is a hydrogen atom can be obtained by activating the compound (IVa) in a solvent in the presence of a base. Can be produced by reacting the resulting alkyl compound.

Examples of the activated alkyl compound include alkyl halides such as alkyl chloride, alkyl bromide and alkyl iodide. Of these, alkyl iodides are preferred. An activated product of an aliphatic alcohol having 2 to 10 carbon atoms represented by the formula HO (CH ₂ ) mOH (where m is an integer of 2 to 10) is also used.

The base used is, for example, an alkali metal hydride such as sodium hydride; an alkali metal alkoxide such as sodium methoxide and potassium butoxide; an alkali metal hydroxide such as sodium hydroxide; hydrogen carbonate Alkali metal carbonates such as sodium and sodium carbonate; trialkylamines such as triethylamine and diisopropylethylamine; aromatic amines such as pyridine; preferably alkali metal hydrides (particularly sodium hydride ).

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent.
Ethers such as ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; esters such as ethyl acetate;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Of these, ethers (particularly tetrahydrofuran) are preferred.

The reaction temperature varies depending on the types of the starting materials, the base and the etherifying agent to be used, but is usually from -20 ° C to 5 ° C.
It is performed at 0 degrees, preferably 0 to 30 degrees.

The reaction time varies depending on the starting materials used, the type of base, the type of etherifying agent and the reaction temperature.
Minutes to 24 hours, preferably 1 to 8 hours.

After the completion of the reaction, the produced ether derivative can be isolated from the reaction solution by a commonly used method.
For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent. In addition, the obtained ether derivative can be purified by means such as distillation, recrystallization, reprecipitation, and column chromatography, if necessary. (Step A-3) Step A-3 is a step of compound (III), compound (IV),
An oxidizing agent is allowed to act on the ether derivative or acyl derivative in the presence of a base in a solvent to form an N-oxyl compound (I)
This is the step of manufacturing.

As the oxidizing agent, an oxidizing agent for converting a secondary amino group into N-oxyl can be used. For example, metal oxide salts such as sodium tungstate and peroxides such as hydrogen peroxide can be used. Can be cited. Preferably, it is a combination of sodium tungstate dihydrate and aqueous hydrogen peroxide. When this combination is used, sodium ethylenediaminetetraacetate tetrahydrate can be used as a catalyst.

Examples of the base include ammonium hydroxides such as triton B (benzyltrimethylammonium hydroxide). Triton B is preferred.

The solvent is not particularly limited as long as it does not hinder the reaction and dissolves the raw materials to some extent. Examples thereof include water, alcohols such as methanol and ethanol, and a mixed solvent thereof. Preferably, it is ethanol or ethanol water.

The reaction temperature varies depending on the type of the starting material, the oxidizing agent, the base and the solvent to be used, but is usually from 0 ° to 50 °, preferably from 10 ° to 30 °.

The reaction time varies depending on the type of starting materials, oxidizing agent, base and solvent used, and the reaction temperature.
Hours to 7 days, preferably 1 to 3 days.

After completion of the reaction, the desired compound (I) can be isolated from the reaction solution by a method usually used. For example, it can be obtained by diluting the reaction solution with water, extracting with an organic solvent such as ether, and distilling off the solvent. Further, the obtained compound (I) can be purified, if necessary, by means such as distillation, recrystallization, reprecipitation, and column chromatography.

[0072]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. (Example 1) (1) Polymerization method: styrene (1 mL), 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-oxopiperidine-N-oxyl (6.5 mmol / L), benzoyl peroxide (BPO ) (5.0 mmol / L) was placed in a glass tube, and the glass tube was degassed using a vacuum line and then sealed.
After heating at 120 ° C for 20 minutes, return to room temperature, 70, 80 and 90
After polymerization at a temperature of ° C for a predetermined time, the content was poured into excess methanol, and the obtained polystyrene was filtered and dried under reduced pressure. When the polymerization system was in a semi-solid state, a small amount of benzene was added to a glass tube to dissolve the contents, and this was poured into methanol to obtain polystyrene.
The conversion was determined by a gravimetric method. The number average molecular weight (M _n ) and polydispersity (M _w / M _n ) were determined by gel permeation chromatography (GPC). (2) GPC measurement conditions: A TOSOH GPC8020 series instrument was used, and TSK _gel G5000HHR, GMultiporeHXL-M and TSK _gel GMHHR-L were used as columns according to the molecular weight of the polymer, and tetrahydrofuran was used as a developing agent. RI for polymer detection
An 8020 refractometer was used. The molecular weight was determined from a calibration curve prepared using a polystyrene standard. (3) Experimental Results FIG. 1 is a plot of the change over time in the degree of polymerization.

FIG. 2 is a plot of the relationship between the degree of polymerization and the molecular weight of polystyrene.

FIG. 3 is a plot of the relationship between the degree of polymerization and the polydispersity of polystyrene.

In this polymerization reaction, the polymerization rate increases linearly with time to a high polymerization rate, and the molecular weight of the obtained polystyrene increases linearly with an increase in the polymerization rate.
Furthermore, the result that the polydispersity was less than 1.3 was obtained. These results show that the growth radical concentration is constant from the start of polymerization to the late stage of polymerization at any reaction temperature, and that the polymerization reaction of styrene proceeds in a living manner. In addition, by this polymerization reaction, even a polystyrene having a high molecular weight exceeding 100,000 could be obtained as a uniform polymer having a small degree of dispersion. (Production Example 1) 2,6-Dispyro-1 ′, 1 ″ -dicyclohexyl-4-o
Synthesis of Xoxopiperidine 10 g of compound (II) obtained in Reference Example 1, ammonium bromide
6.5 g, water 2 ml, cyclohexanone 20 g under nitrogen stream for 24
h stirred. After completion of the reaction, 50% aqueous sodium hydroxide solution 4
0 ml was added, extracted with ether, dried over magnesium sulfate, and then the organic layer was evaporated. Vacuum distillation (5mm
Hg), further isolated by a column, and recrystallized from hexane to obtain the title compound as colorless needle crystals (yield 3.1).
g, 31% yield).

Melting point: 101-103 ° C. (recrystallized from hexane) ¹ H NMR spectrum (CDCl ₃ ) δ / ppm: 1.39 (m, 8H), 1.52
(m, 8H), 1.64 (m, 4H), 2.30 (s, 4H). IR spectrum (KBr): 3300 (NH), 1700 cm ^-1 (C = O). (Production Example 2) 2,6-Dispyro-1 ′, 1 ″ -dicyclohexyl-4-o
Synthesis of Xoxopiperidine -N-oxyl 0.3 g of the compound obtained in Production Example 1, 0.1 g of Triton B and 0.1 g of sodium tungstate dihydrate were added to 10 m of ethanol.
and stirred. There 35% aqueous hydrogen peroxide solution 4.
8 ml was slowly added dropwise, followed by stirring at room temperature for about three days. After completion of the reaction, 100 ml of water was added, and the mixture was extracted with ether. The organic layer was dried over magnesium sulfate, evaporated and recrystallized from ethanol to give the title compound as yellow prism crystals (yield 0.0859 g, 28.6%).

Melting point: 114-116 ° C. (recrystallized from ethanol) IR spectrum (KBr): 1720 cm ⁻¹ (C = O). (Production Example 3) In the production method of the compound of Production Example 1, the following compound is produced by carrying out the same reaction operation using cyclopropanone, cyclobutanone, cyclopentanone or cycloheptanone instead of cyclohexanone. be able to.

2,6-Dispyro-1 ′, 1 ″ -dicyclopropyl-4-oxopiperidine, 2,6-Dispyro-
1 ′, 1 ″ -dicyclobutyl-4-oxopiperidine,
2,6-dispiro-1 ′, 1 ″ -dicyclopentyl-4
-Oxopiperidine, 2,6-dispiro-1 ', 1 "-
Dicycloheptyl-4-oxopiperidine. (Production Example 4) In the method for producing the compound of Production Example 2, the following compound is produced by performing the same reaction operation using the compound obtained in Production Example 3 instead of the compound obtained in Production Example 1. can do.

2,6-Disspiro-1 ′, 1 ″ -dicyclopropyl-4-oxopiperidine-N-oxyl,
6-dispiro-1 ', 1 "-dicyclobutyl-4-oxopiperidine-N-oxyl, 2,6-dispiro-
1 ′, 1 ″ -dicyclopentyl-4-oxopiperidine-N-oxyl, 2,6-dispiro-1 ′, 1 ″ -dicycloheptyl-4-oxopiperidine-N-oxyl. (Production Example 5) 2,6-Dispyro-1 ′, 1 ″ -dicyclohexyl-4-h
Synthesis of droxypiperidine-N-oxyl (1) Compound 2,6-distispiro obtained in Production Example 1
1 mmol of 1 ', 1 "-dicyclohexyl-4-oxopiperidine is dissolved in 10 ml of ethanol, 2 equivalents of sodium borohydride are added at room temperature and the mixture is stirred for 2 hours. The reaction solution is diluted with 50 ml of water and 20 ml of acetic acid is added. Extracted with ethyl, washed with water, dehydrated and concentrated under reduced pressure to give a solid
2,6-Dispiro-1 ′, 1 ″ -dicyclohexyl-4-hydroxypiperidine can be obtained. (2) In the method of Preparation Example 2, the compound obtained in Preparation Example 1 is replaced with (1). The title compound can be produced by using the obtained compound (Preparation Example 5-1) (1) 2,6-Dispyro-1 ′, 1 ″ -dicyclohexyl
Synthesis of 4-hydroxypiperidine Compound 2,6-Dispiro-1 ′, 1 ″ obtained in Production Example 1
After dissolving 1.0 g of dicyclohexyl-4-oxopiperidine in 80 ml of ethanol, 1.0 g of sodium borohydride was dissolved.
Was added and stirred at room temperature for 3 hours. 100 ml of water was added to the reaction solution,
Extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was removed by an evaporator to obtain 0.97 g of 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-hydroxypiperidine. This compound was purified. Used in the next reaction without
A part of this compound was recrystallized from hexane to obtain the following physicochemical data.

Colorless microcrystal Melting point: 93-95 ° C. IR spectrum (KBr): 3280 cm ^-1 (NH and OH) ¹ H-NMR spectrum (CDCL ₃ ) δ ppm: 0.89 (2H, dd, J1)
= J2 = 12.0 Hz), 1.36-1.67 (20H, m), 2.16 (2H, d
d, J = 12.0 and 4.2Hz) 3.98 (1H, tt, J = 12.0 and 4.2)
Hz). (2) 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl
Synthesis of -4-Hydroxypiperidine-N-oxyl Compound 2,6-dispiro-1 ′, 1 ″-obtained in (1)
0.50 g of dicyclohexyl-4-hydroxypiperidine, 1.0 g of triton B and 0.3 of sodium tungstate dihydrate
0 g was dissolved in 10 ml of ethanol, and a 35% aqueous hydrogen peroxide solution 5.
0 ml was added and the mixture was stirred at room temperature for 3 days. 100 ml of water in the reaction solution
After addition, it was extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was removed with an evaporator to give 2,6-dispiro-1 ′,
1 "-dicyclohexyl-4-hydroxypiperidine-N
0.50 g of oxyl were obtained. The crystals of the title compound were obtained by recrystallization from ethyl acetate.

Orange prism crystal Melting point: 176-178 ° C IR spectrum (KBr): 3400 cm ^-1 (OH). (Production Example 6) 2,6-Dispyro-1 ′, 1 ″ -dicyclohexyl-4-a
Synthesis of Sethoxypiperidine-N-oxyl (1) 1 mmol of the compound 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-hydroxypiperidine obtained in (1) of Production Example 5 was dissolved in 5 ml of pyridine, and cooled with ice. Add 2 equivalents of acetic anhydride and stir for 16 hours, add 2 ml of ethanol to the reaction solution and stir at room temperature for 2 hours.
diluted with 20 ml of water, extracted with 20 ml of ethyl acetate, washed with water,
After dehydration and concentration under reduced pressure, solid 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-acetoxypiperidine can be obtained. (2) In the method of Preparation Example 2, The title compound can be prepared by using the compound obtained in (1) in place of the obtained compound (Production Example 7) 2,6-Dispiro-1 ′, 1 ″ -dicyclohexyl-4-. Me
Synthesis of Toxipiperidine-N-oxyl (1) 1 mmol of the compound 2,6-dispiro-1 ′, 1 ″ -dicyclohexyl-4-hydroxypiperidine obtained in (1) of Production Example 5 was dissolved in 10 ml of tetrahydrofuran,
Under ice cooling, 1.1 equivalents of sodium hydride are added, and the mixture is stirred for 2 hours. Then, 5 equivalents of methyl iodide is added, and the mixture is stirred for 8 hours. The reaction solution was diluted with 50 ml of water, extracted with 20 ml of ethyl acetate, washed with water, dehydrated, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give solid 2,6-distispir-1 ′. , 1 "-dicyclohexyl-4-methoxypiperidine. (2) In the method of Preparation Example 2, by using the compound obtained in (1) in place of the compound obtained in Preparation Example 1, (Reference Example 1) 2,2,4,4,6-pentamethyl-2,3,4,5, -tetrahydropi
Synthesis of Limidine (II) 290 g (5 mol) of acetone, 40 g of calcium chloride, and 10 g of ammonium chloride were cooled to -40 ° C in a dry ice-methanol mixed solution, and 110 g of liquid ammonia was stirred.
(6.5 mol) was added. After stirring at room temperature for 24 hours, slowly
Warm to ° C. and dissolve the solid product. Separate the top layer,
The title compound was isolated as a yellow oily liquid by distillation under reduced pressure (5 mmHg) (yield: 82.09 g).

¹ H-NMR spectrum (CDCL ₃ ) δpp
m: 8.90 (6H), 8.64 (6H), 8.13 (2H), 8.04 (3H).

[0083]

By radically polymerizing a radically polymerizable monomer using the N-oxyl compound represented by the formula (I) of the present invention as a mediator, a radical polymerization reaction using an existing mediator can be performed. The polymerization reaction is carried out livingly at a lower reaction temperature,
Even a polymer having a high molecular weight of more than 10,000 could be obtained as a uniform polymer having a small polydispersity. According to the present invention, it is possible to produce a uniform polymer having a desired structure and molecular weight at low cost and with high yield.

[Brief description of the drawings]

FIG. 1 is a plot of the relationship between the reaction time (horizontal axis) and the conversion (vertical axis) in the styrene polymerization reaction of Example 1.

FIG. 2 is a plot of the relationship between the polymerization rate (horizontal axis) and the molecular weight of polystyrene (vertical axis) in the styrene polymerization reaction of Example 1.

FIG. 3 is a graph showing a polymerization rate (horizontal axis) and polydispersity of polystyrene (vertical axis) in the styrene polymerization reaction of Example 1.
This is a plot of the relationship with.

Claims (12)

[Claims] 1. A radical polymerizable monomer represented by the following general formula (I): (Wherein R ¹ and R ² together represent an oxo group, or R ¹ is a hydrogen atom, a hydroxyl group or an amino group,
R ² represents a hydrogen atom; the groups represented by -A- and -B- are the same or different and together with the carbon atom to which they are attached, represent a 3- to 7-membered cycloalkyl group. A) producing a polymer by radical polymerization in the presence of an N-oxyl compound represented by the formula (1) or an ether derivative or an acyl derivative thereof. 2. The method according to claim 1, wherein the polymerization is carried out in the presence of a radical polymerization initiator. 3. The method for producing a polymer according to claim 2, wherein the radical polymerization initiator is a peroxide or an azo compound. 4. The method according to claim 2, wherein the radical polymerization initiator is benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN). 5. The method according to claim 1, wherein the radically polymerizable monomer is a styrene monomer, an acrylic monomer or a methacrylic monomer. 6. A method according to claim 1, wherein the radically polymerizable monomer is a styrene monomer. 7. The N-oxyl compound represented by the formula (I) according to any one of claims 1 to 6, wherein
A method for producing a polymer, wherein the groups represented by-and -B- are a cyclohexyl group together with the carbon atom to which they are bonded. 8. The method according to claim 1, wherein R ¹ of the N-oxyl compound represented by the formula (I) is selected from the group consisting of:
And R ² together are an oxo group, or R ¹ is a hydroxyl group and R ² is a hydrogen atom. 9. The method for producing a polymer according to claim 1, wherein the radical polymerization is started at 100 to 140 degrees Celsius. 10. The method for producing a polymer according to claim 1, wherein the radical polymerization is carried out at a reaction temperature of 70 to 100 degrees Celsius. 11. A compound of the formula (I) A radical polymerization reaction mediator comprising, as an active ingredient, an N-oxyl compound represented by the formula (I) or an ether derivative or an acyl derivative thereof. 12. A compound of the general formula (I) (However, excluding 2,6-dispiro-1 ', 1 "-dicyclohexyl-4-oxopiperidine-N-oxyl), its ether derivative or acyl derivative.