JP2001081079A - Piperazine derivative, its production and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject new compound comprising a specific piperazine derivative, excellent in heat stability and having an antioxidizing ability effective for organic substances. SOLUTION: This compound is represented by formula I (R1 is H, an alkyl or the like; n is 0-2; R2 is a branched alkyl), e.g. 1,4-bis(3-hydroxy-4-tert-butyl-2,6- dimethylbenzyl)piperazine. The compound represented by formula I is produced by reacting a piperazine derivative represented by formula II (e.g. piperazine) with a hydroxybenzyl halide derivative represented by formula III (X is chlorine or bromine) (e.g. 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl chloride) in the presence of a deacidifying agent in an organic solvent, preferably at 40-80 deg.C. N,N- Dimethylformamide, etc., are cited as the solvent and trimethylamine, etc., are cited as the deacidifying agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel piperazine derivative, a method for producing the same, a use thereof, and an organic substance composition containing the same.

[0002]

2. Description of the Related Art In order to prevent deterioration due to oxidation of organic substances such as natural polymers, synthetic polymers, fats and oils, and lubricating oils,
Many antioxidants are currently used. Representative antioxidants include hindered phenol-based, organic sulfur-based, organic phosphorus-based, and aromatic amine-based agents. These are considered effective when used alone or in combination of a plurality of them. Many of the conventionally known antioxidants have excellent antioxidant efficiency, but when kneaded into an organic polymer material and heated and processed, they are partially decomposed or volatilized, or used as a molded product after processing. At this time, there is a problem of volatilization and scattering.

[0003] In order to improve this, by increasing the molecular weight of the antioxidant or adding a non-volatile functional group,
Attempts have been made to improve the shortcomings of volatilization and scattering, but they have not been sufficiently satisfactory in terms of antioxidant efficiency.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel compound having excellent thermal stability per se and having an effective antioxidant ability against various organic substances, and a method for producing the same. It is in.

A second object of the present invention is to provide an organic substance composition containing the novel compound.

[0006]

Means for Solving the Problems A first aspect of the present invention is the following general formula (1):

Embedded image (Wherein R ¹ , R ² and n are the same as described above).

A second aspect of the present invention relates to an antioxidant for organic substances comprising the piperazine derivative according to the first aspect.

A third aspect of the present invention relates to an organic substance composition containing the piperazine derivative according to claim 1.

A fourth aspect of the present invention is the following general formula (2):

Embedded image (Wherein, R ¹ and n are the same as described above), and the following general formula (3)

Embedded image (Wherein R ² is the same as described above), wherein the hydroxybenzyl halide derivative represented by the following general formula (1) is reacted in an organic solvent in the presence of a deoxidizing agent.

Embedded image (Wherein R ¹ , R ² and n are the same as described above).

The above R¹Linear or branched,
Examples of the kill group include a methyl group, an ethyl group and n-propyl.
Group, iso-propyl group, n-butyl group, iso-butyl
Examples thereof include a tyl group, and the number of carbon atoms is 1 to
Three are preferred. The R ²Branched alkyl in
Examples of the group include an iso-propyl group, sec-butyl
Group, tert-butyl group, 1,1-dimethylpropyl
Group, 1,1,3,3-tetramethylbutyl group and the like
But preferably have from 1 to 8 carbon atoms
No.

The solvent used in the reaction of the present invention is usually N, N-dimethylformamide, N, -dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, Examples thereof include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, dichloroethylene, chloroform, and acetates. These are used alone or in combination of two or more. The amount of the solvent used is not particularly limited, and can be appropriately selected depending on the ease of stirring and the solubility of the substrate.

The reaction is carried out at a temperature from room temperature to around the boiling point of the solvent, preferably at 40 to 80 ° C.

As the deoxidizing agent, trimethylamine,
Triethylamine, N, N-dimethylaniline, piperidine, morpholine, pyridine, sodium amide, potassium amide, sodium alkoxide, potassium alkoxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, calcium carbonate And calcium oxide.

The organic substance stabilized by the general formula (1) of the present invention includes poly-α-olefins such as homo- or copolymers of α-olefins such as polyethylene, polypropylene, polybutylene and polyisoprene, and halogens. Vinyl chloride, vinyl esters,
α, β-unsaturated ketones, α, β-unsaturated aldehydes, α, β-unsaturated nitrile acid, α, β-unsaturated acids,
Other esters, dienes, homopolymers or copolymers of unsaturated hydrocarbons such as styrenes, polyols, polyurethanes comprising polyisocyanates,
There are synthetic polymers such as polyamide, polyester, polycarbonate, polyacetal, polystyrene, and polyethylene oxide, semi-synthetic polymers, and polymer materials such as natural polymers.

Other organic substances stabilized by the compounds of the present invention include, for example, animal and vegetable oils used in paints, various volatile oils, natural and synthetic machine oils, mineral oils, fuel oils, cutting oils, waxes and the like. Hydrocarbon-based substances.

The following general formula (1) of the present invention:

Embedded image (Wherein, R ¹ is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group, n is an integer of 0 to 2, and when n is 2, R ¹ is different from each other. R ² is a group selected from the group consisting of branched alkyl groups.) Specific examples of the piperidine derivative represented by the following formula: it can.

1,4-bis (4-tert-butyl-3)
-Hydroxy-2,6-dimethylbenzyl) piperazine, 1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-methylpiperazine, 1,4-bis (4-tert -Butyl-3-hydroxy-2,6-dimethylbenzyl) -2-ethylpiperazine, 1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-n-propylpiperazine , 1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-
iso-propylpiperazine, 1,4-bis (4-te
rt-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-n-butylpiperazine, 1,4-bis (4
-Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-iso-butylpiperazine, 1,4
-Bis (4-tert-butyl-3-hydroxy-2,
6-dimethylbenzyl) -2,3-dimethylpiperazine, 1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-diethylpiperazine, 1,4-bis ( 4-tert-butyl-3
-Hydroxy-2,6-dimethylbenzyl) -2,3-
Di-n-propylpiperazine, 1,4-bis (4-te
rt-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-di-iso-propylpiperazine,
1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-di-n-butylpiperazine, 1,4-bis (4-tert-butyl-
3-hydroxy-2,6-dimethylbenzyl) -2,3
-Di-iso-butylpiperazine, 1,4-bis (4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-dimethylpiperazine, 1,4-bis (4-tert-butyl-3-hydroxy-2,6-
Dimethylbenzyl) -2,5-diethylpiperazine,
1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-n-propylpiperazine, 1,4-bis (4-tert-butyl-3-hydroxy) −2,6-dimethylbenzyl) -2,
5-di-iso-propylpiperazine, 1,4-bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-n-butylpiperazine, 1,4-bis ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-is
o-Butylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl)
Piperazine, 1,4-bis (4-iso-propyl-3)
-Hydroxy-2,6-dimethylbenzyl) -2-methylpiperazine, 1,4-bis (4-iso-propyl-
3-hydroxy-2,6-dimethylbenzyl) -2-ethylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl) -2-
n-propylpiperazine, 1,4-bis (4-iso-
Propyl-3-hydroxy-2,6-dimethylbenzyl) -2-iso-propylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl) -2-n-butyl Piperazine, 1,4
-Bis (4-iso-propyl-3-hydroxy-2,
6-dimethylbenzyl) -2-iso-butylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-dimethylpiperazine, 1,4-bis ( 4-iso-propyl-3
-Hydroxy-2,6-dimethylbenzyl) -2,3-
Diethylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl)-
2,3-di-n-propylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-iso-propylpiperazine, 1,4- Bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-
n-butylpiperazine, 1,4-bis (4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl)
-2,5-di-iso-butylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) piperazine, 1,4-bis (4-se
c-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-methylpiperazine, 1,4-bis (4-se
c-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-ethylpiperazine, 1,4-bis (4-se
c-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-n-propylpiperazine, 1,4-bis (4
-Sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2-iso-propylpiperazine, 1,4
-Bis (4-sec-butyl-3-hydroxy-2,6
-Dimethylbenzyl) -2-n-butylpiperazine,
1,4-bis (4-sec-butyl-3-hydroxy-
2,6-dimethylbenzyl) -2-iso-butylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-dimethylpiperazine, 1,4- Bis (4-sec-butyl-3
-Hydroxy-2,6-dimethylbenzyl) -2,3-
Diethylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-
2,3-di-n-propylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-di-iso-propylpiperazine, 1,4- Bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,3-di-n-
Butylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,
3-di-iso-butylpiperazine, 1,4-bis (4
-Sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-dimethylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2, 5-diethylpiperazine, 1,
4-bis (4-sec-butyl-3-hydroxy-2,
6-dimethylbenzyl) -2,5-di-n-propylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-
iso-propylpiperazine, 1,4-bis (4-se
c-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-n-butylpiperazine, 1,4-bis (4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl) -2,5-di-iso-butylpiperazine, 1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl] -2,3- Dimethylpiperazine, 1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-
Hydroxy-2,6-dimethylbenzyl] -2,3-diethylpiperazine, 1,4-bis [4- (1,1,3,3
3-tetramethylbutyl) -3-hydroxy-2,6-
Dimethylbenzyl] -2,3-di-n-propylpiperazine, 1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl] -2 , 3-di-iso-propylpiperazine,
1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl]
-2,3-di-n-butylpiperazine, 1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-
Hydroxy-2,6-dimethylbenzyl] -2,3-di-iso-butylpiperazine, 1,4-bis [4-
(1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl] -2,5-dimethylpiperazine, 1,4-bis [4- (1,1,3,3- Tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl] -2,5-diethylpiperazine, 1,4-
Bis [4- (1,1,3,3-tetramethylbutyl)-
3-hydroxy-2,6-dimethylbenzyl] -2,5
-Di-n-propylpiperazine, 1,4-bis [4-
(1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethylbenzyl] -2,5-di-is
o-propylpiperazine, 1,4-bis [4- (1,
1,3,3-tetramethylbutyl) -3-hydroxy-
2,6-dimethylbenzyl] -2,5-di-n-butylpiperazine, 1,4-bis [4- (1,1,3,3-tetramethylbutyl) -3-hydroxy-2,6-dimethyl [Benzyl] -2,5-di-iso-butylpiperazine.

The following general formula (2)

Embedded image (In the formula, R ¹ and n are the same as described above.) As specific examples of the compound, the following compound groups can be exemplified.

Piperazine, 2-methylpiperazine, 2-
Ethyl piperazine, 2-n-propyl piperazine, 2-
iso-propylpiperazine, 2-n-butylpiperazine, 2-iso-butylpiperazine, 2,3-dimethylpiperazine, 2,3-diethylpiperazine, 2,3-di-n-propylpiperazine, 2,3-di- iso-propylpiperazine, 2,3-di-n-butylpiperazine,
2,3-di-iso-butylpiperazine, 2,5-dimethylpiperazine, 2,5-diethylpiperazine, 2,5
-Di-n-propylpiperazine, 2,5-di-iso-
Propylpiperazine, 2,5-di-n-butylpiperazine, 2,5-di-iso-butylpiperazine,

The following general formula (3)

Embedded image (In the formula, X represents a chlorine atom or a bromine atom, and R ³ is the same as described above.) As specific examples of the compounds, the following compound groups can be exemplified.

4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl chloride, 4-tert
-Butyl-3-hydroxy-2,6-dimethylbenzyl bromide, 4-iso-propyl-3-hydroxy-2,6-dimethylbenzyl chloride, 4-iso
-Propyl-3-hydroxy-2,6-dimethylbenzyl bromide, 4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl chloride, 4-sec
-Butyl-3-hydroxy-2,6-dimethylbenzyl bromide, 4- (1,1-dimethylpropyl) -3
-Hydroxy-2,6-dimethylbenzyl chloride,
4- (1,1-dimethylpropyl) -3-hydroxy-
2,6-dimethylbenzyl bromide, 4- (1,1,
3,3-tetramethylbutyl) -3-hydroxy-2,
6-dimethylbenzyl chloride, 4- (1,1,
3,3-tetramethylbutyl) -3-hydroxy-2,
6-dimethylbenzyl bromide.

The amount of the compound represented by the general formula (1) of the present invention added to the organic substance varies depending on the type of the organic substance. No matter how much you add, it does not contribute to the improvement of the effect. That is, it is preferably used in a concentration of 0.005 to 5% by weight based on the weight of the organic substance to be stabilized, but is preferably added in an amount of 0.01 to 2% by weight.

The organic polymer substance stabilized by the compound represented by the general formula (1) may further contain, for example, a conventional additive, such as an antioxidant, a light stabilizer, and a metal-free substance. It may contain an activator and a peroxide scavenger.

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol and 2-te
rt-4,6-dimethylphenol, 2,6-di-te
rt-butyl-4-ethylphenol, 2,6-di-t
tert-butyl-4-n-butylphenol, 2,6-
Di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol, 2
-(Α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-dinonyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,4
-Dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1 '-Methyltridec-1'-yl) phenol and mixtures thereof, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6 -Ethylphenol, 2,6-
Didodecylthiomethyl-4-nonylphenol and mixtures thereof, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone,
5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and the like A mixture of 2,4-bis-octylmercapto-6-
(3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-
4-hydroxyanilino) -1,3,5-triazine,
2-octylmercapto-4,6-bis (3,5-di-
tert-butyl-4-hydroxyphenoxy) -1,
3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy)-
1,2,3-triazine, 1,3,5-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, 2,4,6-tris (3,5-di-
tert-butyl-4-hydroxyphenylethyl)-
1,3,5-triazine, 1,3,5-tris (3,5
-Di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine,
1,3,5-tris (3,5-dicyclohexyl-4-
(Hydroxybenzyl) isocyanurate and the like and mixtures thereof, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol),
2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol),
2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-te
rt-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,
2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis [6-
(Α-methylbenzyl) -4-nonylphenol],
2,2'-methylenebis [6-α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,
4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,
6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,
3-tris (5-tert-butyl-4-hydroxy-
2-methylphenyl) butane, 1,1-bis (5-te
rt-butyl-4-hydroxy-2-methylphenyl)
-3-n-dodecyl mercaptan, ethylene glycol bis [3,3'-bis (3'-tert-butyl-4 '
-Hydroxyphenyl) butyrate], bis (3-te
rt-butyl-4-hydroxy-5-methylphenyl)
Dicyclopentadiene, bis [2- (3'-tert-
Butyl-2'-hydroxy-5'-methylbenzyl)-
6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t
ert-4-hydroxyphenyl) propane, 2,2-
Bis (5-tert-butyl-4-hydroxy-2-methylphenyl-4-n-dodecylmercaptan, 1,
1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane and the like and a mixture thereof, 1,3,5-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-ter
t-butyl-4-hydroxybenzyl) -2,3,5
6-tetramethylbenzene, 2,4,6-tris (3,
5-di-tert-4-hydroxybenzyl) -phenol and the like and mixtures thereof, 4-hydroxylauric anilide, 4-hydroxystearic anilide, octyl N- (3,5-di-tert-butyl-4-hydroxy) Phenyl) carbamate and the like and mixtures thereof, dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di -Tert-butyl-4-hydroxybenzylphosphonate, monoethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid calcium salt and the like, and mixtures thereof,
3,5,3 ', 5'-tetra-tert-butyl-4,
4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-ter
t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-te
rt-butyl-4-hydroxybenzyl) sulfide,
Isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate and the like and mixtures thereof, dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-
4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl 2,2-bis (3,5-di-
tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert)
-Butyl-4-hydroxybenzyl) malonate and the like, and mixtures thereof, esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols; Examples include, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol. Pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, - hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2]
Octane and the like, and mixtures thereof, β- (5-tert
-Butyl-4-hydroxy-3-methylphenyl) propionic acid and esters of the following monohydric or polyhydric alcohols; examples of alcohols include, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and the like, and mixtures thereof, β
Esters of-(3,5-dicyclohexyl-4-hydroxy) propionic acid with the following monohydric or polyhydric alcohols; examples of alcohols include, for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and the like, and mixtures thereof;
Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols; examples of alcohols include, for example, methanol, ethanol, octadecanol, 1,6-hexanediol , 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol,
Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and the like, and mixtures thereof;
N, N'-bis (3,5-di-tert-butyl-4-
(Hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert- Butyl-4-hydroxyphenylpropionyl) hydrazine and the like, and mixtures thereof.

As the light stabilizer, for example, 2- (2'-
Hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-
Hydroxyphenyl) benzotriazole, 2- (5 ′
-Tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5'-
(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-
Butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '
-Hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ',
5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- [3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl] benzotriazole, 2- [3 '-Tert-butyl-2'-hydroxy-5'-(2'-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-
[2- (2-ethylhexyloxycarbonylethyl)
-2'-hydroxyphenyl] -5-chlorobenzotriazole, 2- [3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-
tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylmethyl) phenyl] benzotriazole, 2- [3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) Phenyl] benzotriazole, 2- {3'-tert-butyl-5 '-[2- (2-ethylhexyloxycarbonylethyl) -2'-hydroxyphenyl]} benzotriazole, 2- (3'-dodecyl-2'-Hydroxy-5'-methylphenyl) benzotriazole, 2-
[3'-tert-butyl-2'-hydroxy-5'-
(2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-
[Hydroxyphenyl] benzotriazole and a transesterified product of polyethylene glycol 300 and a mixture thereof, 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy -, 4,2 ', 4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy- or 4- (2-ethylhexyloxy)-
Hydroxybenzophenone derivatives and the like and mixtures thereof, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-
-Butylbenzoyl) resorcinol, 2,4-di-t
tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,
5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4
-Hydroxybenzoate, 2-methyl-4,6-di-
tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and the like and mixtures thereof, ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α -Carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline And mixtures thereof, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3 , 5-di-tert
-Butyl-4-hydroxybenzylmalonate, 4,
4'-dioctyloxyoxanilide, 2,2'-diethoxyoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,
2,2'-didodecyloxy-5,5'-di-tert
-Butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide And mixtures thereof, and 2-ethoxy-
Mixtures with 2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, mixtures of o- and p-ethoxy-disubstituted oxanilides, etc .: 2,4 , 6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-
Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2
-Hydroxy-4-propyloxyphenyl) -6-
(2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and the like can be mentioned.

As the metal deactivator, for example, N,
N'-diphenyloxamide, N-sartilal-N'-
Salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-ter
t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazine, N, N '-Diacetal adipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N-bis (salicyloyl) thiopropionyl dihydrazide, triphenyl phosphite, diphenylalkyl phosphite, tris (nonylphenyl) phosphite , Trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-
Di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis [2,4,6-tris (tert-butylphenyl)] pentaerythritol diphosphite, tristearylsorbitol phosphite, tetrakis (2,4 -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6
-Isooctyloxy-2,4,8,10-tetra-t
ert-butyl-12H-dibenz [d, e] -1,
3,2-dioxaphosphosine, 6-fluoro-2,4,
8,10-tetra-tert-butyl-12-methyl-
Dibenz [d, g] -1,3,2-dioxaphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-t
tert-butyl-6-methylphenyl) ethyl phosphite and the like, and mixtures thereof.

Examples of the peroxide scavenger include dilauryl, distearyl, dimyristyl or ditridecylthiodipropionate, zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (β- (Dodecyl mercapto) propionate and the like.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples of the present invention. However, these are merely examples of preferred embodiments, and the present invention is not limited thereto.

Example 1 11.0 g (45.8 mmol) was added to 20 ml of chloroform.
l) 4-tert-butyl-3-hydroxy-2,6
4.95 g (48.9 m) over 20 minutes while adding dimethylbenzyl chloride and stirring at 20 ° C. or less.
mol) of triethylamine (15 ml) in chloroform. After the addition, 2.0 g (2
A solution of 3.1 mmol) of piperazine in 15 ml of chloroform is added dropwise at 30 ° C. or lower over 30 minutes.
Shortly after the end of the dropping, a precipitate can be seen. 20-25 ° C
After stirring for 3 hours at, the precipitate was filtered off with suction.
After washing with 0 ml of n-hexane / chloroform (1: 1), washing with water and drying, the desired 1,4-bis (3-hydroxy-4-tert) having a melting point of 247.5-248.5 ° C.
4.38 g of (t-butyl-2,6-dimethylbenzyl) piperazine are obtained. The filtrate and washing solvent are combined and then concentrated to give a solid. This is 30m
l of dimethylformamide (DMF), 50 ml of 1,
When recrystallized from a mixed solvent consisting of 4-dioxane and 15 ml of water, the melting point was further increased to 247.5 to 248.5 ° C.
Was obtained in an amount of 5.34 g. The total mass is 9.7
The yield is 86% at 2 g. The identification data of this is as follows.

Mass spectrometry: (m / z) 467 (M ⁺⁺ 1,
25%), 277 (14), 276 (21), 275
(100), 191 (60), 190 (56), 175
(19), 149 (14), 135 (21), 87 (1
5).

Infrared absorption spectrum: cm ^-1 (KBr)
3569, 3436 (OH), 2949, 2801 (alkyl group), 1408, 1218 (CO), 1174
(CN).

Example 2 11.0 g (45.8) was added to 20 ml of 1,4-dioxane.
mmol) of 4-tert-butyl-3-hydroxy-
While adding 2,6-dimethylbenzyl chloride and stirring at 20 ° C or lower, 4.95 g (48.
9 mmol) of triethylamine in 5 ml of 1,4
-Dioxane is added dropwise. After dropping, 2.0 g more
A solution of (23.1 mmol) piperazine in 60 ml of 1,4-dioxane is added dropwise at 30 ° C. or lower over 30 minutes. After completion of the dropwise addition, stirring is continued at 70 to 75 ° C. for 1 hour, followed by cooling. The precipitate is filtered off with suction and 10m
Wash with 1 of 1,4-dioxane. The filtrate and washings are combined and then concentrated to give a solid. This product was recrystallized with a mixed solvent consisting of 30 ml of DMF, 50 ml of 1,4-dioxane and 15 ml of water to give 1,4-bis (the target compound having a melting point of 247.5 to 248.5 ° C.). 9. 3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) piperazine.
15 g were obtained. The yield is 90%.

Example 3 1.26 g of 2,5-dioxane was added to 20 ml of 1,4-dioxane.
Dimethylpiperazine (11 mmol) and 2.23 g
Of triethylamine (22 mmol) was added, and 40 to 4
Stir while maintaining 5 ° C. If a clear liquid is obtained,
Remove heater and continue stirring until cooled to room temperature. Upon reaching room temperature, 5.0 g (22 mmol) of 4-ter
A solution of t-butyl-3-hydroxy-2,6-dimethylbenzyl chloride diluted with 5 ml of 1,4-dioxane is added dropwise over 5 minutes. After dropping, leave at room temperature for 1 hour.
After stirring for an hour, the mixture is further heated and stirred at 95 to 100 ° C. for 2 hours. After cooling, the precipitate was filtered off with suction and 10 m
Wash with 1 l, 4-dioxane, then with 100 ml water and n-hexane. 289.5-290.5
1,4-bis (3-hydroxy-4)
-Tert-butyl-2,6-dimethylbenzyl)-
5.38 g of 2,5-dimethylpiperazine was obtained. The crude yield is 99%. The identification data of this is as follows.

Mass spectrometry: (m / z) 495 (M ⁺⁺ 1,
14%), 304 (15), 303 (65), 248
(51), 234 (12), 192 (16), 191
(100), 190 (34), 175 (14), 149
(19), 135 (26).

Infrared absorption spectrum: cm ^-1 (KBr)
3559, 3430 (OH), 2952, 2791 (alkyl group), 1409, 1217 (CO), 1175
(CN).

Example 4 To an unstabilized polypropylene powder, 0.1% by weight of the compound of the present invention obtained in Example 1 was added, and the mixture was sufficiently mixed with a mixer under a nitrogen atmosphere. Next, the mixture is extruded at 260 ° C. using a screw type extruder, and pelletized with a pelletizer. MFR of the obtained pellet at 230 ° C. (JIS
K6758) was measured. Table 1 shows the results. M
FR represents the index of the molecular weight, the smaller the value,
This indicates that the molecular weight is significantly reduced by oxidative deterioration in the extruder. This indicates that the antioxidant effect is large.

The obtained pellets were compression molded at 230 ° C. into a sheet having a thickness of 0.5 mm to prepare a test piece. The heat aging resistance was measured by heating a test piece in a circulating air oven at 150 ° C. and measuring the time required until the test piece became yellowed and embrittled by oxidative deterioration.

In the weather resistance test, the sheet was irradiated with light from a xenon lamp in a weatherometer at a black panel temperature of 80 ° C., and the time required for cracking of the test piece due to bending was measured. did.

[0039]

[Table 1]

[0040]

(1) According to the present invention, a novel compound which itself has excellent thermal stability and is useful as an antioxidant for various organic substances, and a method for producing the same can be provided. (2) According to the present invention, a novel organic substance composition stabilized against oxidation can be provided.

Claims (4)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ is a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group, n is an integer of 0 to 2, and when n is 2, R ¹ is different from each other. the good .R ² even groups, piperazine derivatives represented by a member selected from the group consisting of alkyl group branched group.). 2. An antioxidant for an organic substance comprising the piperazine derivative according to claim 1. 3. An organic substance composition comprising the piperazine derivative according to claim 1. 4. The following general formula (2): (Wherein R ¹ and n are the same as described above), and a piperazine derivative represented by the following general formula (3): Wherein X represents a chlorine atom or a bromine atom, and R ² is the same as defined above, wherein the hydroxybenzyl halide derivative is reacted in an organic solvent in the presence of a deoxidizing agent. The following general formula (1) (In the formula, R ¹ , R ² and n are the same as described above.)