JP3446312B2 - Production method of polyaminotriazine - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an efficient process for producing polyaminotriazine which is useful as a light stabilizer for organic materials, particularly synthetic resins. More specifically, formula (I):

[0002]

[Wherein n represents a number of 2 to 20; X ¹ ,
X ² , X ³ and X ⁴ are each independently hydrogen or the formula (I
a):

[0004]

(In the formula, R ¹ is hydrogen, a hydroxyl group, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 18 carbon atoms, an alkenyl having 3 to 8 carbon atoms, and a carbon atom having 7 to 1 carbon atoms.
1 represents arylalkyl or alkenyloxy having 3 to 5 carbon atoms).
At least 75 mol% of the total of X ¹ , X ² , X ³ and X ⁴ is the piperidyl; R represents an alkylene having 2 to 12 carbon atoms, and the alkylene is —O— or —NR ² — (formula Wherein R ² represents hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, or piperidyl of the formula (Ia)), or R represents the number of carbon atoms. 6 to 15 represents a divalent alicyclic group; and Q represents a formula —OR ³ , —NHR ⁴ , or —NR ⁴ R ⁵ (wherein R ³ represents an alkyl group having 1 to 12 carbon atoms, a carbon atom). Cycloalkyl, benzyl, phenyl, tolyl of the formulas 5-12 or the formula (I
a) piperidyl, R ⁴ is alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms, N, N-dialkylaminoalkyl having 4 to 12 carbon atoms, and 3 to 5 carbon atoms. Represents alkenyl, phenyl, benzyl, cyclohexyl, tolyl or piperidyl of formula (Ia), and R ⁵ represents alkyl or cyclohexyl having 1 to 12 carbon atoms, or R ⁴ and R ⁵ are attached to them. 5- or 6-membered -O together with nitrogen atom
-Or-NH-, which forms a heterocyclic ring which may be included in the middle thereof).].

[0006]

2. Description of the Related Art It is known that organic materials such as synthetic resins such as polyethylene and polypropylene are deteriorated by light and are accompanied by phenomena such as softening, embrittlement or discoloration, and their physical properties are deteriorated. Various light stabilizers have been conventionally used for the purpose of preventing such deterioration. The polyaminotriazine represented by the formula (I) is known as such a light stabilizer.

Compounds of formula (I), especially X ¹ , X ² , X
Compounds in which ³ and X ⁴ are piperidyl of formula (Ia) are generally of formula (II):

[0008]

(Wherein R and R ¹ have the same meanings as described above) and dipiperidyldiamine of the formula (III):

[0010]

[0011] (wherein, Q is as defined above) (JP 52-71486 JP is prepared by polycondensation reaction of dichlorotriazinyl emission represented by the JP 58
− 201820 publication).

Further, the dipiperidyldiamine of the formula (II) usually has the formula (IIa):

[0013]

Tetramethylpiperidone represented by the formula (wherein R ¹ has the same meaning as described above) and formula (IIb): NH ₂ —R—NH ₂ (IIb) (wherein R is as defined above). Diami represented by
It is prepared by reacting the emission (JP-B-58 -
11454, JP-A-5-86029, etc.).

The production of the dipiperidyldiamine of the formula (II) and the production of the polyaminotriazine of the formula (I) have heretofore been carried out completely independently, and the production of the polyaminotriazine of the formula (I) The isolated dipiperidyl diamine of formula (II) was used. However, in the production and isolation of the dipiperidyldiamine of the formula (II), loss is unavoidable to some extent, and therefore, the tetramethylpiperidone of the formula (IIa) or the diamine of the formula (IIb) is used as a reference for formula (I) It was the current situation that the total yield of obtaining the polyaminotriazine was not necessarily high.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to remedy these drawbacks of the prior art and to provide a process for the efficient production of polyaminotriazines of formula (I). Another object of the present invention is to provide a method for efficiently producing high-quality polyaminotriazine.

[0017]

The present inventors have conducted research to develop an efficient method for producing polyaminotriazine, and as a result, tetramethylpiperidone of the formula (IIa) and the formula
From the crude product obtained from the reaction of (IIb) with diamine, the formula (I
It was found that the polyaminotriazine of formula (I) can be produced in good yield by carrying out a polycondensation reaction of the diamine of formula (I) with dichlorotriazine of formula (III) without isolation, and further The present inventors have found that high-quality polyaminotriazine of formula (I) can be produced in good yield by using a specific amount of tetramethylpiperidone of (IIa), and completed the present invention.

[0018] The present invention, tetramethyl piperidone and diamine of formula (IIb) is reductive alkylation amination reaction in the presence of a reducing hydrogenation catalyst of formula (IIa), was obtained by removing the catalyst after the reaction Subjecting the crude product (A) to a polycondensation reaction with the dichlorotriazine of the formula (III) in the presence of an inorganic base in an aromatic solvent without purification , and also of the formula (I
Per mole of diamine of Ib), tetramethylpyrrole of formula (IIa)
Use peridone in the range of more than 1.5 mol and less than 2.0 mol
It is intended to provide a method of polyaminotriazine of formula (I), wherein.

In the formula (I), X ¹ , X ² , X ³ and /
Alternatively, the arylalkyl represented by R ¹ when X ⁴ is piperidyl of formula (Ia) can typically be phenylalkyl. The divalent alicyclic group represented by R in the formula (I) may have a cycloalkane ring, and includes, for example, cycloalkylene, methylenedicycloalkylene, cycloalkylenemethylene and the like. , May be substituted with alkyl within the number of carbon atoms defined above. If -NR ⁴ R ⁵ represented by Q in formula (I) to form a 5- or 6-membered heterocycle, a group -NR composed according heterocyclic ⁴
Specific examples of R ⁵ are 1-pyrrolidinyl, 1-imidazolidinyl, piperidino, 1-piperazinyl, morpholino and the like.

One of the starting materials, tetramethylpiperidone of formula (IIa), in which R ¹ is hydrogen or methyl, is particularly useful.

Another starting material of formula (II
The diamine of b) is particularly useful when R is ethylene or hexamethylene. The present invention includes not only the embodiment in which the diamine of the formula (IIb) is used alone, but also the embodiment in which it is mixed with 20% by weight or less of water.

Tetramethylpiperidone of formula (IIa) and the formula
The diamine (IIb) is industrially produced and is easily available.

As the reductive hydrogenation catalyst in the reductive alkyl amination reaction, platinum, nickel, cobalt, palladium and the like can be used. Among these, platinum, palladium or nickel, specifically platinum or palladium supported on carbon (hereinafter, platinum /
Carbon, palladium / carbon) and Raney nickel are useful. Usually, when platinum or palladium is used, the amount of tetramethylpiperidone of the formula (IIa) from 0.001 to
When Raney nickel is used in the presence of 0.04% by weight of catalyst at 40-140 ° C., 10% of tetramethylpiperidone of formula (IIa) in the presence of 0.1-30% by weight of catalyst is used.
The reductive alkyl amination reaction is carried out at 0 to 180 ° C.

In the reductive alkyl amination reaction, the formula (I
Tetramethylpiperidone of Ia) is the diamine 1 of formula (IIb)
About 2 mol is usually used per mol. In the known literature as well, for the purpose of completing the reaction, tetramethylpiperidone of the formula (IIa) was used in an amount of 2.0 mol or a slight excess thereof per mol of the diamine of the formula (IIb). However, the product obtained by reacting 2.0 moles or more of the tetramethylpiperidone of the formula (IIa) with 1 mole of the diamine of the formula (IIb) in this manner can be purified without purification. When the polycondensation reaction with the dichlorotriazine of)) is performed, the obtained polyaminotriazine of the formula (I) may be colored reddish brown. The products colored in this way tend to be disliked in applications of light stabilizers for organic materials, and have poor commercial value. It is considered that the cause of this coloration is that the slightly remaining tetramethylpiperidone of the formula (IIa) is partially decomposed and colored during the polycondensation reaction and the post-treatment.

Therefore, according to the present invention, when the crude product obtained by the reductive alkylamination reaction is used as it is for the subsequent polycondensation reaction, in the reductive alkylamination reaction, per 1 mol of the diamine of the formula (IIb), Ru used in an amount of less than 2.0 mole of tetramethyl piperidone of formula (IIa). As described above, when the tetramethylpiperidone of the formula (IIa) is used in a slightly insufficient manner, since the polyaminotriazine of the formula (I) obtained by the polycondensation reaction in the latter stage is hardly colored, the commercial value is maintained. Be drunk However, if the amount of the tetramethylpiperidone of the formula (IIa) is too small, the effective performance of the finally obtained polyaminotriazine of the formula (I) as a light stabilizer decreases. Therefore, in the present invention, the amount of tetramethylpiperidone of the formula (IIa) is 1.5 mol or more and less than 2.0 mol per 1 mol of the diamine of the formula (IIb).
To use. In particular, per mole of diamine of formula (IIb),
It is preferred to use tetramethylpiperidone of formula (IIa) in the range 1.7 to 1.95 mol.

Tetramethylpiperidone of formula (IIa) and formula (II
The reaction of b) with a diamine can be carried out according to a known reductive alkyl amination method. For example, methanol,
Using ethanol, propanol or a mixture of the alcohols and water as a solvent, a reductive alkyl amination reaction of tetramethylpiperidone of the formula (IIa) and a diamine of the formula (IIb) is performed in the presence of platinum, palladium or Raney nickel. The method is useful because there are few by-products other than the monopiperidyl compound and the crude product can be subjected to the polycondensation reaction only by distilling the solvent off from the filtrate after removing the catalyst by filtration. Specifically, for example
A method similar to that described in JP-A-58-11454, that is, a method of using methanol as a solvent and reacting in the presence of platinum / carbon or palladium / carbon at 55 to 70 ° C. and a hydrogen pressure of 9 to 10 atm for 4 to 5 hours is described. Can be taken.

Further, a method similar to that described in JP-A-5-86029, that is, tetramethylpiperidone of the formula (IIa) and a diamine of the formula (IIb) and 50 to 100 ° C. in the absence of a solvent are used.
At the same time, the product obtained by distilling off water in the reaction system under reduced pressure, for example, at 1 to 135 Torr is reacted with hydrogen in the presence of platinum, palladium or Raney nickel to give a reduced alkyl. The method of carrying out the amination reaction is very useful because the crude product can be directly subjected to the polycondensation reaction as it is by simply removing the catalyst by filtration.
Specifically, for example, without using a solvent, tetramethylpiperidone of the formula (IIa) and diamine of the formula (IIb) are mixed in an amount of 50 to 60.
The mixture was heated at 60 ° C for 1 hour and further reacted at 60 ° C and 30 Torr for 3 hours, and at the same time, water in the system was distilled off to obtain a mixture, and the mixture was mixed with platinum / carbon or palladium / carbon for 90 hours.
℃, a method of reacting at 5 atm hydrogen pressure for 4 hours, or using decanted Raney nickel, 100 ℃, hydrogen pressure 100
A method of reacting at atmospheric pressure for 4 hours can be adopted.
In these cases, as mentioned above, the diamine 1 of formula (IIb)
1.5 mol of tetramethylpiperidone of formula (IIa) per mol
When used in an amount of not less than 2.0 mol and less than 2.0 mol, high-quality polyaminotriazine can be obtained through the polycondensation reaction.

In the crude product (A), the main component is the formula
A product obtained by reacting two molecules of tetramethylpiperidone of the formula (IIa) per molecule of the diamine (IIb) and the diamine 1
A product obtained by reacting one molecule of the tetramethylpiperidone is included per molecule. Even when tetramethylpiperidone of the formula (IIa) purified to a purity of 99% by weight or more by a method such as distillation or recrystallization is used, for example, N- (2-propyl) -N is used as a by-product. ′-(2,2
6,6-Tetramethyl-4-piperidyl) hexamethylenediamine and the like are included in an amount of less than 1% by weight. If these trace amounts of by-products also have a functional group capable of reacting with dichlorotriazine, they will be included as a unit of the polyaminotriazine of the formula (I).
Does not have any effect on the performance of the polyaminotriazine.

Examples of the dichlorotriazine of the formula (III) used in the polycondensation reaction, when Q is -NHR ⁴ may, R ⁴
Particularly useful are those wherein is a straight chain or branched alkyl having 4 to 8 carbon atoms. When Q is -NR ⁴ R ⁵ ,
It is useful that R ⁴ and R ⁵ together with the nitrogen atom form a morpholine ring. Specific examples of particularly useful dichlorotriazines of formula (III) include 2,4-dichloro-6
-(1,1,3,3-tetramethylbutylamino)-
1,3,5-triazine, 2,4-dichloro-6-morpholino-1,3,5-triazine and the like can be mentioned.

The dichlorotriazine of the formula (III) can be produced by a known method, for example, the method described in JP-A-52-71486. Specifically, it can be produced by a reaction with cyanuric chloride and a monofunctional compound of the formula (IV): QH (IV) (Q has the same meaning as described above). The solution after the reaction can be used for the present invention without isolating the dichlorotriazine of the formula (III) formed. of course,
This dichlorotriazine can be used after being isolated by a known method such as a recrystallization method.

By adjusting the amount of dichlorotriazine of the formula (III) used in the polycondensation reaction, the degree of polymerization of the polyaminotriazine of the formula (I) can be controlled.
In the present invention, the compound of the formula (II
The dichlorotriazine of I) is generally used in an amount of 0.75 to 1 mol, preferably 0.8 to 0.9 mol. When the amount used is less than 0.75 mol, a large amount of polyaminotriazine having a low polymerization degree, in which n in the formula (I) is less than 5, is produced. When used for a synthetic resin or the like that is used outdoors for a long period of time, n having a higher polymerization degree of 6 or more, particularly about 7 to 11, is desired. On the other hand, if it is used in excess of 1 mol, the reaction will not be completed.

In the present invention, the inorganic base is used in the reaction as a solid or as an aqueous solution. The reaction can be carried out by using an organic base such as triethylamine, but in this case, n in the formula (I) is less than 6 and only a product having a relatively low degree of polymerization is obtained, and the yield is Cause a decrease in.

As the inorganic base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkali metal carbonates such as sodium carbonate and potassium carbonate are preferably used, and sodium hydroxide or potassium hydroxide is particularly preferably used. To be done.

The inorganic base is preferably used in the range of 2 to 3 equivalents, particularly 2.2 to 2.5 equivalents relative to the dichlorotriazine of the formula (III). The amount of inorganic base is of formula (III)
When the amount is less than 2 equivalents to the dichlorotriazine, the reaction is difficult to complete. Further, if it exceeds 3 equivalents, it is economically disadvantageous.

The aromatic solvent used in the polycondensation reaction may be any solvent which is inert to the reaction and immiscible with water. Examples of such a solvent include xylene, ethylbenzene,
Toluene, ortho-dichlorobenzene, mesitylene, etc. may be mentioned. However, when an aromatic solvent having a high boiling point of 170 ° C. or higher under atmospheric pressure such as ortho-dichlorobenzene is used, it is necessary to operate at high temperature and high vacuum in order to remove the solvent from the reaction mixture. Therefore, an aromatic solvent having a relatively low boiling point, for example, a boiling point in the range of about 100 to 160 ° C. under atmospheric pressure, specifically, xylene, ethylbenzene, toluene, or a mixed solvent of two or three of these. Etc. are preferably used. Among them, xylene, ethylbenzene or a mixed solvent thereof is preferable. In order to carry out the operation smoothly, the solvent is usually used in an amount of 0.1 times by weight or more the crude product (A).

The polycondensation reaction can be carried out at a temperature of 80 ° C. or higher, but in the temperature range of 145 to 220 ° C., especially 15
It is preferably carried out in a temperature range of 5 to 190 ° C. 145 ° C
When it is less than 1, the reaction time becomes long and the polymerization degree is often lowered, the by-products are increased and / or the yield is often lowered. Above 220 ° C, decomposition reaction of raw materials and products may occur.

The polycondensation reaction can be carried out in various modes as long as the above-mentioned aromatic solvent and inorganic base are used. For example, it can be carried out by mixing the inorganic base, the crude product (A) and the dichlorotriazine of the formula (III) at room temperature and then maintaining the temperature at a predetermined reaction temperature. In order to suppress the formation of by-products, a method of adding the dichlorotriazine of the formula (III) at a predetermined reaction temperature to the solution of the crude product (A) in which the inorganic base is dispersed is suitable. . In these methods, the dichlorotriazine of formula (III) is
Usually used as a solution. In this case, the compound is
The isolated product may be used by dissolving it in a desired solvent, but it is preferable to use the prepared solution, that is, the reaction mixture obtained by reacting cyanuric chloride with the compound of the formula (IV) in the solvent. Efficient and preferred.

The polycondensation reaction can be carried out under pressure or under atmospheric pressure.

For example, when the autoclave is used under pressure, the reaction temperature suitable for the present invention can be easily achieved regardless of the amount of the aromatic solvent used. In this case, it is preferable to use the inorganic base as its concentrated aqueous solution. For example, in an autoclave, a mixture of the crude product (A) and a 50% aqueous solution of sodium hydroxide or potassium hydroxide is kept in the temperature range of 145 to 220 ° C., where the aromatic dichlorotriazine of the formula (III) is used. A polyaminotriazine of the formula (I) can be produced by slowly dropping a solvent solution and conducting a polycondensation reaction under pressure.

When the reaction is carried out under atmospheric pressure, the formula (III)
When an aromatic solvent solution of dichlorotriazine is added, water in the reaction system such as water produced in the reaction and, if necessary, part of the solvent are distilled off to maintain the reaction temperature suitable for the present invention. It becomes possible. Here, a solid inorganic base is used as the inorganic base.

In the polycondensation reaction under atmospheric pressure, a powder or flake of sodium hydroxide or potassium hydroxide is preferably used as the solid inorganic base. Especially sodium hydroxide is preferably used.

In the polycondensation reaction under atmospheric pressure, 190
Attempts to achieve a reaction temperature above 0 ° C usually tend to reduce the amount of solvent that can be used, resulting in poor operability. Therefore, the polycondensation reaction under atmospheric pressure is 145
It is preferably carried out in the temperature range of ˜190 ° C., especially 155˜180 ° C., using 0.1 to 1 times, especially 0.2 to 0.8 times the weight of the crude product (A).

When the polycondensation reaction is carried out at atmospheric pressure, the formula (I
When the solution of dichlorotriazine of II) is added, a part of the solvent is distilled off together with water in the reaction system in order to maintain a predetermined reaction temperature. The addition of the solution of dichlorotriazine of formula (III) is carried out, for example, by slowly adding the solution dropwise over time. By adopting such means, a predetermined reaction temperature can be maintained, and at the time when the solution of the dichlorotriazine of the formula (III) has been added dropwise, the crude product (A) can be used in an amount of 0.1 to 1
A weight amount of solvent can be achieved. The condition that the amount of the aromatic solvent is 0.1 to 1 times the weight of the crude product (A) should be achieved at the stage where the main reaction proceeds. Thus, for example, 1 for the crude product (A)
Even when a solution of the dichlorotriazine of the formula (III) containing a solvent in excess of weight times is charged, a part of the solvent is distilled off during the addition, so that the solvent amount of the crude product (A The embodiment in which the range is 0.1 to 1 times the weight of the above) also satisfies this condition. After the addition of the solution of the dichlorotriazine of formula (III) is completed, the water in the reaction system is distilled off azeotropically while maintaining the predetermined reaction temperature to complete the reaction.

As described above, the advantage of removing water in the reaction system by azeotropic dehydration is that it is possible to use a SUS 316L reactor in addition to maintaining a high reaction temperature under atmospheric pressure. It is in.

After the reaction is complete, the reaction mixture is washed with water, dried and filtered. Filtration is facilitated by the addition of filter aids such as cellulose, diatomaceous earth or fuller's earth. Evaporation of the solvent of the filtrate gives the polyaminotriazine of formula (I) as a mass which is solid at room temperature and can be optionally ground.

Specific examples of the particularly useful polyaminotriazine of the formula (I) thus obtained include the following. It should be noted that the components contained in the crude product (A) in an amount of less than 1% by weight are not described here, but these examples may naturally contain such components as a part of the unit.

N- (2,2,6,6-tetramethyl-4
-Piperidyl) hexamethylenediamine and N, N'-
A mixture of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1,3. Polycondensation product of 5-triazine, N- (2,
2,6,6-Tetramethyl-4-piperidyl) hexamethylenediamine and N, N'-bis (2,2,6,6-
A mixture of tetramethyl-4-piperidyl) hexamethylenediamine and 2,4-dichloro-6-morpholino-1,
Polycondensate of 3,5-triazine, N- (1,2,2,2
6,6-Pentamethyl-4-piperidyl) hexamethylenediamine and N, N'-bis (1,2,2,6,6-
A mixture of pentamethyl-4-piperidyl) hexamethylenediamine and 2,4-dichloro-6- (1,1,3,3
-Tetramethylbutylamino) -1,3,5-triazine polycondensate, N- (1,2,2,6,6-pentamethyl-4-piperidyl) hexamethylenediamine and N,
N'-bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) hexamethylenediamine mixture and 2,4
-Polycondensation product of dichloro-6-morpholino-1,3,5-triazine and the like.

[0048]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified,% in the examples is based on weight.

Example 1: Preparation of (a) intermediate: 2,2,6,6-tetramethyl-4-in an autoclave
Piperidone (94.6 g, 0.609 mol), hexamethylenediamine (37.3 g, 0.321 mol), methanol (20
0 g) and 5% platinum / carbon (0.55 g) were charged, and the temperature was kept at 65 ° C for 3 hours at a hydrogen pressure of 9 to 10 atm, and then at 70 ° C for 1 hour. After completion of the reaction, the catalyst was filtered and methanol was distilled off under reduced pressure to obtain 119.7 g of a concentrated mass. In this case, 2,2,6,6-tetramethyl-4
The charge molar ratio of piperidone to hexamethylenediamine corresponds to 1.9: 1. The mass was analyzed by gas chromatography to find that N, N'-bis (2,2,2
The content of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine is 94.4% and that of N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine is 5.4%. I found out.

(B) Preparation of dichlorotriazine: 20 g of water and cyanuric chloride (52.3 g, 0.284) were put in a flask.
mol) and mixed xylenes (boiling point 138-141 ° C) 13
Charge 0 g and keep it at 8-10 ℃ 1,1,3,3
-Tetramethylbutylamine (37.5g, 0.290mol)
Was slowly added dropwise. Next, while maintaining at 8-10 ℃, 20
57.9 g of an aqueous sodium hydroxide solution was slowly added dropwise. After completion of the reaction, oily water was separated to remove the aqueous phase.

(C) Preparation of polyaminotriazine: The above (a) was placed in a flask equipped with a Dean Stark trap.
The total amount of the concentrated mass of the intermediate obtained in 1 above and powdery sodium hydroxide (28.4 g, 0.71 mol) were charged, and the temperature was raised to 160 ° C. Next, 2,4-dichloro-6-prepared in (b) above
(1,1,3,3-tetramethylbutylamino) -1,
A solution of 3,5-triazine in xylene was added dropwise to the mixture over 4 hours. After the start of the dropping, an increase in the internal temperature was observed, and when the dropping was continued for a while, the water produced in the reaction was distilled off and at the same time reflux of xylene was observed. Then, since the internal temperature began to drop, a part of the refluxed xylene was distilled off so that the internal temperature did not drop below 160 ° C. At the end of the dropping, the amount of xylene distilled off was 88 g, and the amount of xylene in the reaction solution was 0.35 weight times that of the concentrated mass (119.7 g). After completion of the dropwise addition, the temperature of the mixture was kept at 160 ° C. for 5 hours while distilling off water produced by the reaction. After the reaction was completed, water was added to dissolve and remove sodium chloride produced in the reaction. The xylene solution is filtered to remove by-products and then concentrated, and the remaining melt is cooled to 1
66.3 g of solid resin was obtained, which was ground.

Yield 92% Number average molecular weight 4900 n = 7.5

Example 2 (a) Preparation of Intermediate: The same operation as in Example 1 (a) was repeated except that the temperature was kept at 65 ° C. for 3 hours instead of 60 ° C. for 3.5 hours. Upon application, 120.1 g of concentrated mass was obtained. In this square,
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) hexamethylenediamine 87.0%, N-
The content of (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine was 12.1%.

(C) Preparation of polyaminotriazine: The concentrated mass obtained in (a) above and 2,4-dichloro-6- (1,1,3,3) prepared in the same manner as in Example 1 (b). -Tetramethylbutylamino) -1,3,5-triazine solution was used in the same manner as in Example 1 (c) to obtain 164.7 g of a solid resin, which was crushed. At this time, when the dropping of the xylene solution of 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine was completed, the amount of xylene distilled off was 87 g.
Thus, the amount of xylene in the reaction solution was 0.36 times the weight of the concentrated mass.

Yield 91% Number average molecular weight 4400 n = 6.7

Example 3: (a) Preparation of intermediate: 2,2,6,6-tetramethyl-4-piperidone
Using 9.6 g (0.577 mol), the same operation as in Example 1 (a) was performed except that the temperature of 65 ° C. was changed to 59 ° C. to obtain 115.3 g of concentrated mass. . In this case, the charged molar ratio of 2,2,6,6-tetramethyl-4-piperidone and hexamethylenediamine corresponds to 1.8: 1. In this square, N, N'-bis (2,2,2
6,3-Tetramethyl-4-piperidyl) hexamethylenediamine was 80.3%, and N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine was 1%.
It was included in 9.4%.

(B) Preparation of dichlorotriazine: 20 g of water and cyanuric chloride (50.0 g, 0.271) were placed in a flask.
mol) and mixed xylene 125g, 8-10 ℃
While maintaining at 1, 1,1,3,3-tetramethylbutylamine (35.9 g, 0.278 mol) was slowly added dropwise. Next, while maintaining the temperature at 8 to 10 ° C, 55.5 g of a 20% aqueous sodium hydroxide solution was slowly added dropwise. After completion of the reaction, oily water was separated to remove the aqueous phase.

(C) Production of polyaminotriazine: The concentrated mass obtained in (a) above, sodium hydroxide (27.2)
g, 0.68 mol) and 2,4-dichloro-obtained in (b) above.
6- (1,1,3,3-tetramethylbutylamino)-
The same operation as in Example 1 (c) was performed except that a xylene solution of 1,3,5-triazine was used, to obtain 161.7 g of a solid resin, which was pulverized. At this time, 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino)
At the end of the addition of the xylene solution of -1,3,5-triazine, the amount of xylene distilled off was 85 g, and the amount of xylene in the reaction solution was 0.35 weight times that of the concentrated mass.

Yield 93% Number average molecular weight 3700 n = 5.5

Example 4: (a) Preparation of intermediate: 2,2,6,6-tetramethyl-4-piperidone
Using 3.6 g (0.603 mol), the temperature was kept at 65 ℃.
The same procedure as in Example 1 (a) was performed except that the temperature was kept at ℃, to obtain 119.4 g of concentrated mass. In this case 2,
The charged molar ratio of 2,6,6-tetramethyl-4-piperidone and hexamethylenediamine corresponds to 1.88: 1. N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine contained 94.6% and N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine contained 4.8%.

(C) Production of polyaminotriazine: An autoclave was charged with the total amount of the concentrated mass of the intermediate obtained in the above (a) and 56 g of 50% aqueous sodium hydroxide solution, and the mixture was heated to 180 ° C. Next, 2,4-dichloro-6- (1,1,1) prepared in the same manner as in Example 1 (b)
A xylene solution of 3,3-tetramethylbutylamino) -1,3,5-triazine was added dropwise to the mixture over 4 hours. An increase in the internal temperature was observed after the start of dropping, and when the dropping was continued for a while, pressurization inside the reactor was observed. After the completion of dropping, the temperature was kept at 180 ° C. for 5 hours. After the reaction,
The aqueous sodium chloride solution produced in the reaction was separated and removed. The xylene solution was filtered to remove by-products and then concentrated, and the remaining melt was cooled to obtain 165.6 g of a solid resin, which was crushed.

Yield 92% Number average molecular weight 4700 n = 7.2

Example 5: (a) Preparation of intermediate: 2,2,6,6-tetramethyl-4-piperidone (92.2 g, 0.594 mol) and hexamethylenediamine (37.3 g, 0) were placed in a flask. .321mol), 50-60 ℃
After incubating at 60 ° C for 1 hour, it was dehydrated at 30 Torr 60 ° C for 3 hours. The reaction mass was transferred to an autoclave, charged with 5% platinum / carbon (0.55 g), and kept at 90 ° C. for 4 hours under a hydrogen pressure of 5 atm. When the catalyst was filtered after the reaction was completed,
121.9 g of reaction product was obtained. In this case 2,
The charged molar ratio of 2,6,6-tetramethylpiperidone and hexamethylenediamine corresponds to 1.85: 1. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine was added to this mass in an amount of 9
The content was 2.2% and 7.5% of N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine.

(C) Preparation of polyaminotriazine: In place of the concentrated mass of the intermediate in Example 4 (c), the above
162.3 g of a solid resin was obtained by the same procedure as in Example 4 (c) except that the entire amount of the reaction product obtained in (a) was used, and this was pulverized.

Yield 91% Number average molecular weight 4800 n = 7.0

Example 6: (a) Preparation of intermediate: 2,2,6,6-tetramethyl-4-piperidone
The same operation as in Example 5 (a) was performed except that 4.7 g (0.610 mol) was used to obtain 121.0 g of a reaction product. In this case, the charged molar ratio of 2,2,6,6-tetramethylpiperidone and hexamethylenediamine corresponds to 1.9: 1. N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine was 95.1% and N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine was 4.5%.

(C) Preparation of polyaminotriazine: 2,4-dichloro-prepared as in Example 1 (b).
6- (1,1,3,3-tetramethylbutylamino)-
Example 1 (c) except that a xylene solution of 1,3,5-triazine was used and the total amount of the reaction product obtained in (a) above was used instead of the concentrated mass of the intermediate in Example 1 (c). The same operation as in (16) was performed to obtain 168.4 g of a solid resin, which was crushed. At this time, 2,4-dichloro-6- (1,1,3,3
-Tetramethylbutylamino) -1,3,5-triazine at the end of the addition of the xylene solution, the amount of xylene distilled off was 89 g, which was 0.3 in the reaction solution with respect to the diamine.
Four times the weight of xylene was achieved.

Yield 93% Number average molecular weight 4700 n = 7.2

Reference example 1 : (a) Preparation of intermediate: 2,2,6,6-tetramethyl-4-piperidone was added to 10
The same procedure as in Example 1 (a) was performed, except that 4.6 g (0.674 mol) of the mixture was kept at 65 ° C. instead of being kept at 61 ° C. to obtain 129.1 g of concentrated mass. It was In this case, the charged molar ratio of 2,2,6,6-tetramethylpiperidone and hexamethylenediamine corresponds to 2.1: 1. N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine was contained at 97.6% and 2,2,6,6-tetramethylpiperidone at 2.0%, but N- (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine was not detected.

(B) Preparation of dichlorotriazine: 53.0 g (0.287 mol) of cyanuric chloride, 132 g of mixed xylene, 38.0 g (0.294 mol) of 1,1,3,3-tetramethylbutylamine, 20 The same operation as in Example 1 (b) was conducted except that 58.8 g of a 5% aqueous sodium hydroxide solution was used, and 2,4-dichloro-6- (1,1,3,3-
Tetramethylbutylamino) -1,3,5-triazine was prepared.

(C) Production of polyaminotriazine: 28.8 g of the concentrated mass obtained in (a) above, sodium hydroxide
Use (0.72mo l), and the prepared 2,4-dichloro-6- (1,1,3,3-tetramethylbutyl) -1,3,5-triazine xylene solution (b) The same operation as in Example 1 (c) was carried out except that 175.9 g was used.
Of solid resin was obtained and was crushed. At this time, when the dropping of the xylene solution of 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine was completed, the amount of xylene distilled off was 88 g, In the reaction solution, 0.34 times as much xylene as diamine was achieved.

Yield 92% Number average molecular weight 7200 n = 11.4

Reference Example 2 : Coloring degree of polyaminotriazine: Regarding the polyaminotriazines obtained in Examples 1 to 6 and Reference Example 1 , the light transmittance of the solution was measured under the following conditions. The results are shown in Table 1. Higher transmittance means that the hue of polyaminotriazine is closer to colorless and transparent.

Measurement conditions: (1) Preparation of sample: 1.0 g of polyaminotriazine was dissolved in 10 ml of toluene, and filtered with a membrane filter. (2) Measuring conditions of equipment: Model: U-3400 type self-recording spectrophotometer manufactured by Hitachi, Ltd. Measurement wavelength: 300 to 600 nm Scan speed: 120 nm / min

[0075]

[Table 1]

[0076]

According to the present invention, the tetramethyi of the formula (IIa)
In the reaction of a certain amount of lupiperidone with the diamine of formula (IIb)
Dichloro of formula (III) without purification of the resulting intermediate
High quality due to polycondensation reaction with triazine
The polyaminotriazine of formula (I) can be efficiently produced in high yield.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-2-218678 (JP, A) JP-A-58-201820 (JP, A) JP-A-57-58681 (JP, A) JP-A-51- 126240 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 73/00-73/26

Claims (12)

(57) [Claims] 1. Formula (I): Wherein, n represents the number of 2 to 20; the X ^1, X ^2, X ³ and X ⁴ are each independently hydrogen or formula (Ia): (In the formula, R ¹ is hydrogen, hydroxyl group, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, arylalkyl having 7 to 11 carbon atoms or carbon atom. And represents at least 75 mol% of the total of X ¹ , X ² , X ³ and X ⁴ is piperidyl; and R is 2 to 12 carbon atoms. represents alkylene, the alkylene is -O- or -NR ² - (wherein, R ² is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, or the formula (Ia) Piperidyl) or R represents a divalent alicyclic group having 6 to 15 carbon atoms; and Q is of the formula —OR ³ , —NHR ⁴ , or —NR ⁴ R ⁵ (In the formula, R
³ is alkyl having 1 to 12 carbon atoms, 5 to 1 carbon atoms
2 represents cycloalkyl, benzyl, phenyl, tolyl or piperidyl of the formula (Ia), wherein R ⁴ has 1 to 1 carbon atoms.
2 alkyl, C 3-12 alkoxyalkyl, C 4-12 N, N-dialkylaminoalkyl, C 3-5 alkenyl, phenyl, benzyl, cyclohexyl, tolyl or formula (Ia) It represents piperidyl, and either R ⁵ represents an alkyl or cyclohexyl having 1 to 12 carbon atoms, or R ⁴ and R ^5, 5-membered together with the nitrogen atom to which they are attached or 6-membered -O -Or-NH-, which forms a heterocycle which may be included in the middle thereof), is a process for producing a polyaminotriazine represented by the formula (IIa): (In the formula, R ¹ has the same meaning as described above) and tetramethylpiperidone represented by the formula (IIb): NH ₂ —R—NH ₂ (IIb) (wherein R has the same meaning as described above). Diami
The crude product (A) obtained by the reductive alkyl amination reaction of benzene in the presence of a reduction hydrogenation catalyst and removing the catalyst after the reaction is completed without purification in an aromatic solvent in the presence of an inorganic base. Formula (III): (Wherein, Q is as defined above) is subjected to polycondensation reaction between dichlorotriazine represented by, and the formula (I
Per mole of diamine of Ib), tetramethylpyrrole of formula (IIa)
Use peridone in the range of more than 1.5 mol and less than 2.0 mol
Wherein the. 2. A formula (I) in which R ¹ is hydrogen or methyl, R is a straight-chain or branched alkylene having 2 to 12 carbon atoms and Q is a group —NHR ⁴ or —NR ⁴ R ^5. The method according to claim 1, wherein the polyaminotriazine is produced. 3. A process according to claim 2 for preparing a polyaminotriazine of formula (I) in which Q is the group --NHR ⁴ . 4. A polyaminotriazine of formula (I) wherein R ¹ is hydrogen, R is hexamethylene and Q is 1,1,3,3-tetramethylbutylamino. Method. 5. A compound of formula (III) per mole of diamine of formula (IIb).
Dichlorotriazine of 0.75 to 1 mol is used.
The method according to any one of claims 1 to 4 . 6. The crude product (A) is prepared according to the formula (I) in the absence of a solvent.
Ia) tetramethylpiperidone with diamine of formula (IIb)
The reaction is carried out at a temperature of 50 to 100 ° C.
The product obtained by distilling off water under reduced pressure was treated with platinum and para.
By reacting with hydrogen in the presence of dium or Raney nickel
The reductive alkyl amination reaction is performed, and then the catalyst is removed.
The obtained product according to any one of claims 1 to 5.
Way . 7. The crude product (A) is methanol or ethanol.
, Propanol or a mixture of the alcohol and water
Used as a solvent, the presence of platinum, palladium or Raney nickel.
Of tetramethylpiperidone of formula (IIa) and formula (IIb)
Reductive alkyl amination reaction with diamine and contact
It is obtained by removing the solvent by filtration and then distilling off the solvent.
Item 6. The method according to any one of Items 1 to 5 . 8. 0.0 of tetramethylpiperidone of formula (IIa).
4 in the presence of 01-0.04% by weight platinum or palladium
Claim to carry out reductive alkyl amination reaction at 0 to 140 ° C
Item 8. The method according to any one of Items 1 to 7 . 9. 0.1 of tetramethylpiperidone of formula (IIa)
30 100-18 under existence of wt% of Raney nickel
A reductive alkyl amination reaction is carried out at 0 ° C.
The method described in any one of . 10. A crude product (A) in an autoclave and
Of a 50% aqueous solution of sodium hydroxide or potassium hydroxide
Incubate the mixture in the temperature range 145-220 ° C, where
A solution of dichlorotriazine of formula (III) in an aromatic solvent
A method in which polycondensation reaction is carried out under pressure by slowly dropping the solution.
9. The method according to any of 9 . 11. A crude product (A) and solid water at atmospheric pressure.
145 to a mixture of sodium oxide or potassium hydroxide
Insulate in the temperature range of 190 ℃,
Slowly drop the aromatic solvent solution of lolotriazine,
Polycondensation while distilling off water and some aromatic solvents in the reaction system
The method according to claim 1, wherein the reaction is performed . 12. As the inorganic base, sodium hydroxide or
1 mol of dichlorotriazine of the formula (III)
Any one of claims 1 to 11, which is used in an amount of 2 to 3 mol.
The method described in .