JPH115790A - Polyaminotriazine mixture, its production and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve bleed resistance and allow liquid feed when using a specific polyaminotriazine mixture as a stabilizer for organic materials such as polyethylene or polypropylene by using the specific polyaminotriazine mixture. SOLUTION: This polyaminotriazine mixture is represented by formula I [X<1> to X<4> are each 2,2,6,6-tetramethyl-4-piperidyl or H; at least either one of X<1> and X<2> and at least either one of X<3> and X<4> are each 2,2,6,6-tetramethyl-4- piperidyl; Y and Z are each H or 4,6-bis(1,1,3,3-tetramethylbutylamino)-1,3,5- triazin-2-yl; (n) is 0-20] (with the proviso that >=5% of the total amount of the Y and Z is 4,6-bis(1,1,3,3-tetrabutylamino)-1,3,5-triazin-2-yl). The mixture is produced by reacting a compound represented by formula II with a compound represented by formula III and a diamine represented by formula IV (at least either one of X and X<5> is 2,2,6,6-tetramethyl-4-piperidyl and the other is H) in a specific proportion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyaminotriazine mixture, a method for producing the same and a use thereof.

[0002]

2. Description of the Prior Art Polyaminotriazine mixtures are known as light stabilizers for organic materials such as polyethylene and polypropylene. 1 to 1.2 for dichlorotriazine and dichlorotriazine
A method of reacting a diamine in a molar amount of about one-half is known (JP-A-52-71486, JP-B-4-4329).
. However, since the polyaminotriazine mixture obtained by the above method has a high melting point, it is difficult to mix it with an organic material by a liquid feed, and it has to be fed in a powder form. In the working environment, and the problem of weighability in continuous feeding. The present inventors have conducted intensive studies to provide a polyaminotriazine mixture free of such problems, and as a result, a specific polyaminotriazine mixture obtained by reacting not only dichlorotriazine but also monochlorotriazine with diamine is a liquid. While exhibiting a low melting point that can be fed, the polyaminotriazine mixture, when incorporated in an organic material,
They found that bleeding was difficult, and completed the present invention.

[0003]

[Means for Solving the Problems]

That is, the present invention provides a compound represented by the formula (I)

(Wherein X ¹ , X ² , X ³ and X ⁴ each represent a 2,2,6,6-tetramethyl-4-piperidyl group or hydrogen, and at least one of X ¹ and X ² And at least one of X ³ and X ⁴ represents a 2,2,6,6-tetramethyl-4-piperidyl group, and Y and Z are each hydrogen or 4,6-bis (1,1,
(3,3-tetramethylbutylamino) -1,3,5-triazine-2-
Represents an yl group. n represents an integer of 0 to 20. ) Wherein at least 5% of the total amount of Y and Z in the mixture is 4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5 Formula (II) in the presence of a practically excellent polyaminotriazine mixture characterized by being a -triazin-2-yl group and a base and an organic solvent

[0006] A dichlorotriazine represented by the formula (III):

[0007] And the monochlorotriazine (II) and the monochlorotriazine (III) in an amount of 0.5 to 2 mol times the total amount of the formula (IV)

X—NHC ₆ H ₁₂ NH—X ⁵ (IV) (wherein X and X ⁵ are each 2,2,6,6-tetramethyl-4
-Represents a piperidyl group or hydrogen, at least one of which is 2,
Represents a 2,6,6-tetramethyl-4-piperidyl group. Wherein the diamine represented by the formula (I) is reacted
The present invention provides an industrially excellent method for producing a polyaminotriazine mixture represented by the formula (1) and uses thereof.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Dichlorotriazine (II) and monochlorotriazine (III) used as raw materials of the present invention are produced, for example, by reacting cyanuric chloride with octylamine according to the method described in JP-A-52-71486. I can do it. Dichlorotriazine (II) and monochlorotriazine
(III) may be used by taking it out of the reaction mass or without taking it out. Of course, both may be separated and used after being taken out, or the separated product may be further purified by a purification method such as recrystallization.

As dichlorotriazine (II), for example,
2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino)-
1,3,5-triazine, 2,4-dichloro-6- (n-octylamino) -1,3,5-triazine, a mixture thereof and the like, and 2,4-dichloro-6- (1 , 1,3,3-Tetramethylbutylamino) -1,3,5-triazine is preferred. As monochlorotriazine (III), for example, 2-chloro-4,6-bis (1,
1,3,3-tetramethylbutylamino) -1,3,5-triazine, 2-chloro-4,6-bis (n-octylamino) -1,3,5-triazine, mixtures thereof and the like. But 2-chloro
-4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,
5-Triazine is preferred. Monochlorotriazine (III)
Is generally used in an amount of 0.1 to 10 moles, preferably 0.25 to 5 moles, based on dichlorotriazine (II). here,
If less than 0.1 mole times, the melting point is high, for example, about 11
A polyaminotriazine mixture exceeding 0 ° C. is obtained, and if it exceeds 10 mol times, the obtained polyaminotriazine mixture tends to bleed from the organic material contained therein.

Diamine (IV) which is another raw material
Is, for example, triacetoneamine and octylamine,
It can be produced by reacting according to the method described in JP-A-64-50858. The diamine (IV) can be used without isolation from the reaction mass, but is preferably used after isolation. Of course, those isolated and purified by a purification method such as distillation and recrystallization are also preferably used. As the diamine (IV), for example, N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine, N- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, mixtures thereof and the like. Among them, it is preferable to use the former alone or a mixture in which the latter is １ ／ mole times or less of the former, whereby a polyaminotriazine mixture having better performance as a light stabilizer is obtained. The diamine (IV) is used in an amount of about 0.5 to 2 times, preferably about 1 to 2 times, the total amount of dichlorotriazine (II) and monochlorotriazine (III). Here, when it is less than 0.5 mole times and more than 2 mole times, the obtained polyaminotriazine mixture tends to bleed from the organic material contained.

As the base, inorganic bases such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkali metal carbonates such as sodium carbonate and potassium carbonate are preferably used. The base is usually used in an amount of about 1 to 3 equivalents based on the total amount of dichlorotriazine (II) and monochlorotriazine (III). If the amount used is less than 1 equivalent, the reaction tends to be difficult to complete, and even if it exceeds 3 equivalents, almost no effect is observed at the amount exceeding the equivalent, which is economically disadvantageous.

The organic solvent is not particularly limited as long as it is inert to the reaction, but an organic solvent that is immiscible with water is preferable, and an aromatic solvent is particularly preferable. Examples of such aromatic solvents include toluene, xylene, ethylbenzene, mesitylene, o-dichlorobenzene,
And the like. Among them, xylene and ethylbenzene are preferably used. The amount of the organic solvent used is usually about 0.1 to 5 times by weight based on the diamine (IV),
It is preferably about 0.2 to 1.5 times by weight.

[0014] The reaction is usually carried out at a temperature of 140 ° C or higher. Preferably 140 ° C to 220 ° C, more preferably 155 ° C
~ 180 ° C. If the reaction is performed at a temperature lower than 140 ° C, the reaction is slow and it takes a long time to complete the reaction.
It is usually carried out at the above temperature. The reaction is carried out under normal pressure,
It can be carried out either under pressure or under reduced pressure, preferably while removing generated water.

The resulting polyaminotriazine mixture is
For example, the reaction mass can be taken out from the reaction mass by washing with water, filtering if necessary, and then distilling off low boiling components.

Thus, n is from 0 to 20;
At least one of the groups Y and Z is 4,6-bis (1,1,3,3-tetra
Methylbutylamino) -1,3,5-triazin-2-yl group
Polyaminotriazine blend containing polyaminotriazine
A compound is obtained. Wherein the terminal groups Y and Z are
Hydrogen or 4,6-bis (1,1,3,3-tetramethylbutyla
Mino) -1,3,5-triazin-2-yl group,
4,6-bis (1,1,3,3-tetramethylbutyla
(Mino) -1,3,5-triazin-2-yl group
The retention rate is preferably 5% or more, more preferably 15% or more.
Above, especially 30% or more is preferable. Such value
Is calculated from the peak intensity of the mass spectrum, for example.
obtain. Also X¹, X^Two, X^Three, X^FourAre 2,2,6,
6-tetramethyl-4-piperidyl group or hydrogen, but X
¹And X^TwoAt least one of X and X^ThreeAnd X^FourAt least
One is a 2,2,6,6-tetramethyl-4-piperidyl group.
X¹, X^Two, X^Three, X ^Four75% or more of the total of
It is preferably a 6,6-tetramethyl-4-piperidyl group.
New Also, the polyaminotriazine mixture of the present invention
Gel permeation analysis (GPC) based on styrene
The average molecular weight is determined, and from this value, Y and Z are both hydrogen.
The average degree of polymerization calculated as described above is preferably 3 or less.
More preferably, it is 0.2-3, especially 0.3-2.
Preferably, there is. Polyaminotriazine blend of the present invention
The compound has a melting point at which liquid feed is possible, for example, about 30 to 110 ° C.
It has a melting point in the range of degrees.

The organic materials which can be stabilized by using the polyaminotriazine mixture of the present invention include, for example, the following materials, each of which can be used alone or a mixture of two or more. Although it is possible, it is not limited to these organic materials.

(1) Polyethylene, for example, low density polyethylene (LD-PE), high density polyethylene (HD-P)
E), linear low density polyethylene (LLD-PE),
(2) polypropylene, (3) ethylene / propylene copolymer, (4) methylpentene polymer, (5) EEA (ethylene / ethyl acrylate copolymer) resin, (6) EVA (ethylene / vinyl acetate copolymer) resin (7) ethylene / vinyl alcohol copolymer resin, (8) polystyrenes such as polystyrene, poly (p-methylstyrene), poly (α-
(9) AS (acrylonitrile / styrene copolymer) resin, (10) ABS (acrylonitrile /
Butadiene / styrene copolymer) resin, (11) AAS (special acrylic rubber / acrylonitrile / styrene copolymer)
Resin, (12) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, (13) chlorinated polyethylene, polychloroprene, chlorinated rubber, (14) polyvinyl chloride, polyvinylidene chloride, (15) methacrylic resin, (1
6) Fluororesin, (17) polyacetal, (18) grafted polyphenylene ether resin and polyphenylene sulphite resin, (19) polyurethane, (20) polyamide, (21) polyethylene terephthalate, polybutylene terephthalate, (22) polycarbonate, ( 23) Polyacrylate, (24) Polysulfone, polyetheretherketone, polyethersulfone, (25) Aromatic polyester resin, (26) Epoxy resin (27) Diallylphthalate prepolymer, (28) Silicone resin, (29) Saturated polyester resin, (30) acrylic-modified benzoguanamine resin, (31) benzoguanamine / melamine resin, (32) urea resin,

(33) polybutadiene, (34) 1,2-polybutadiene, (35) polyisoprene, (36) styrene / butadiene copolymer, (37) butadiene / acrylonitrile copolymer, (38) silicone rubber, 39) epichlorohydrin rubber, (40) acrylic rubber, (41) natural rubber,

(42) Chlorine rubber paint, (43) Polyester resin paint, (44) Urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paint,
(48) amino alkyd resin paint, (49) alkyd resin paint, (50) nitrocellulose resin paint, (51) oil-based paint,
(52) Wax, (53) Lubricating oil, etc.

Among these, organic materials which are particularly suitable for stabilization with the polyaminotriazine mixtures according to the invention are low-density polyethylene (LD-PE), high-density polyethylene (HD-PE) and linear low-density polyethylene ( LLD-PE), and synthetic resins such as polypropylene, EVA resin, and ethylene / propylene copolymer.

When the polyaminotriazine mixture of the present invention is blended with an organic material, the amount of the blend is as follows.
It is usually about 0.01 to 5 parts by weight with respect to 00 parts by weight. The organic material containing the polyaminotriazine mixture may further contain other additives as necessary, such as a phenolic antioxidant, a sulfuric antioxidant, a phosphorus antioxidant, an ultraviolet absorber, and a hindered amine other than the present invention. Contains light stabilizers, lubricants, plasticizers, halogen-based or phosphorus-based flame retardants, nucleating agents, metal deactivators, antistatic agents, pigments, inorganic fillers, epoxy compounds, adsorption inhibitors, decolorizing agents, etc. You can also. Of course, these additives can be blended simultaneously with the polyaminotriazine mixture of the present invention, or can be blended at a different stage from the polyaminotriazine mixture.

In blending the polyaminotriazine mixture of the present invention or other optional additives with an organic material, any known method and apparatus for obtaining a homogeneous mixture can be used. For example, when the organic material is a solid polymer, the polyaminotriazine mixture or further optional additives can be directly blended with the solid polymer, or the polyaminotriazine mixture or further optional additives can be added in the form of a masterbatch. , Solid polymers. If the organic material is a synthetic polymer,
The polyaminotriazine mixture or a solution or dispersion of an optional additive may be added to the polymer solution during or immediately after the polymerization. On the other hand, when the organic material is a liquid such as oil, the polyaminotriazine mixture or an optional additive can be directly added and dissolved, or the polyaminotriazine mixture or an optional additive can be dissolved in a liquid medium. Alternatively, they can be added in a suspended state.

[0024]

According to the present invention, there can be provided a polyaminotriazine mixture having a melting point capable of being fed into a liquid, for example, a melting point of about 30 to 110 ° C. In addition, the mixture is excellent in practical use because it has excellent bleed resistance.

[0025]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The percentages and parts in the examples are by weight unless otherwise specified. The terminal capping ratio was determined from the mass spectrum (MS) peak intensity by the following formula. Terminal capping rate = [(One of Y, Z
4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5-
The sum of the MS peak intensities of a compound having a triazin-2-yl group and the other being hydrogen + (Y and Z are both 4,6-bis (1,1,3,3-tetramethylbutylamino) -1, 3,5-triazin-2-yl group: sum of MS peak intensities of compound) × 2] / ｛[(sum of MS peak intensities of compound in which both Y and Z are hydrogen) + (one of Y and Z) Is 4,
6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5-triazin-2-yl The sum of the MS peak intensities of the compounds in which the other is hydrogen) + (Y, Z Both are 4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5-triazin-2-yl groups and the sum of the MS peak intensities of the compounds)] × 2｝ × 100

Reference Example 1 200 g of xylene, 80 g of water and 80 g of cyanuric chloride were placed in a flask, and stirred at 10 ° C., 57.2 g of 1,1,3,3-tetramethylbutylamine and 37.6 g of a 48% aqueous sodium hydroxide solution.
Was added over 3 hours. Then, the temperature was raised to 40 ° C., and 21.3 g of 1,1,3,3-tetramethylbutylamine and 48%
After adding 15 g of aqueous sodium hydroxide solution over 30 minutes, the mixture was stirred at 40 ° C. for 1 hour. After cooling to room temperature and separating the aqueous layer, 2-chloro-4,6-bis- (1,1,3,3-
Contains 0.17 mol of tetramethylbutylamino) -1,3,5-triazine and 0.26 mol of 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine 334 g of a xylene solution was obtained.

Example 1 A flask equipped with a stirrer and Dean-Stark trap was charged with 196.9 g of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and sodium hydroxide powder 43.4 g was charged and the temperature was raised to 160 ° C. with stirring. Next, the xylene solution 3 obtained in Reference Example 1 was added thereto.
34 g were added over 4 hours. Since the internal temperature began to drop during the addition, part of the refluxing xylene was distilled off so that the internal temperature did not drop below 160 ° C. After adding the xylene solution, stirring was continued at the same temperature for 5 hours while removing distilled water, and then cooled to room temperature. Next, water was added thereto, and the mixture was stirred. After that, the aqueous layer was removed, the organic layer was filtered, and the filtrate was concentrated to obtain 275 g of a solid. The melting point of this
At 63 to 70 ° C, mass spectrometry of the product revealed that the maximum molecular weight was 5783 and n was calculated to be 9 at the maximum. The number average molecular weight determined by GPC was 699, and the average degree of polymerization was 0.52.
It was calculated. The terminal blocking rate was 33%.

Example 2 In Example 1, N, N′-bis (2,2,6,6-tetramethyl
196.9 g of -4-piperidyl) hexamethylenediamine,
43.4 g of powdered sodium hydroxide as xylene solution
0.09 mol of 2-chloro-4,6-bis- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine and 2,4-dichloro-6-
Except that 325 g of a xylene solution containing 0.34 mol of (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine was used, 252 g of a solid was obtained in the same manner as in Example 1. Obtained. It has a melting point of 90-96 ° C and a maximum molecular weight of
6974, and n was calculated to be a maximum of 11. The number average molecular weight determined by GPC was 882, and the average degree of polymerization was calculated to be 0.82. The terminal sealing rate was 34%.

Comparative Example 1 In Example 1, N, N'-bis (2,2,6,6-tetramethyl
454 g of -4-piperidyl) hexamethylenediamine, 100 g of sodium hydroxide in powder form, 461 g of xylene as a xylene solution and 2,4-dichloro-6- (1,1,3,3-tetramethylbutylamino) -1, Except for using a solution consisting of 279 g of 3,5-triazine,
620 g of a solid were obtained. It had a melting point of 115-121 ° C., a maximum molecular weight of 9388, and n was calculated to be a maximum of 15. The number average molecular weight determined by GPC was 1819, and the average degree of polymerization was calculated to be 2.4.

Examples 3, 4 and Comparative Example 2 (Evaluation of bleed resistance) Unstabilized homopolypropylene resin was mixed with calcium stearate and tetrakis [methylene-3].
-(3,5-di-t-butyl-4-hydroxybutyl) propionate] methane and 0.05 parts of tris (2,4-di-t-butylphenyl) phosphite, respectively, and the polyaminotriazine mixture obtained above 0.2 parts were added, and the mixture was granulated by an extruder at 230 ° C., and a 1 mm thick sheet was prepared by an injection molding machine at 230 ° C. Place the resulting sheet in an oven at 80 ° C for 7
After a period of days, the bleed resistance was evaluated by measuring the gloss value (60 ° specular gloss). The higher the gloss value, the better the bleed resistance.

[0031]

Table 1 Polyaminotriazine gloss value Example 3 Example 1 94.8 Example 4 Example 2 89.2 Comparative Example 2 Comparative Example 1 75.6

Examples 5, 6 and Comparative Examples 3, 4, 5 (Evaluation of weather resistance) Unstabilized polyethylene resin (LLD-PE)
In addition, the polyaminotriazine mixture produced above and CY
ASORB UV-3346 (manufactured by Scitech, melting point 110-130 ° C)
Was added and granulated with an extruder at 200 ° C., and this was formed into a film having a thickness of 20 μm by an inflation machine at 200 ° C. The obtained polyethylene film was stretched outdoors, and weather resistance was evaluated in days until the tensile elongation in the tensile test became half of the initial value. Table 1 shows the results.

[0033]

TABLE 2] half-life examples of polyaminotriazine added pressure amount tensile elongation 5 Example 2 0.1 (parts) 100 (days) Example 6 Example 2 0.2 130 Comparative Example 3 Comparative Example 1 0.1 95 Comparative Example 4 Comparative Example 1 0.2 120 Comparative Example 5 UV-3346 0.2 100

Claims (14)

[Claims] (1) Formula (I) (Wherein X ¹ , X ² , X ³ , and X ⁴ are 2,2,6,6-
Represents a tetramethyl-4-piperidyl group or hydrogen, X ¹
At least one of the at least one of X ² and X ³ and X ⁴ and represents a 2,2,6,6-tetramethyl-4-piperidyl group.
Y and Z each represent hydrogen or a 4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5-triazin-2-yl group. n represents an integer of 0 to 20. ), Wherein Y and Z in the mixture are
Is a 4,6-bis (1,1,3,3-tetramethylbutylamino) -1,3,5-triazin-2-yl group in an amount of 5% or more of the total amount of polyaminotriazine. 2. The method according to claim 1, wherein X ¹ , X ² , X ³ , X
^At least 75 mol% of the total of ⁴ is 2,2,6,6-tetramethyl-4
The polyaminotriazine mixture according to claim 1, which is a piperidyl group. 3. The method according to claim 1, wherein the melting point is in the range of 30 to 110.degree.
3. The polyaminotriazine mixture according to 2. 4. A compound of the formula (II) in the presence of a base and an organic solvent. A dichlorotriazine represented by the formula (III): X-NHC ₆ H ₁₂ NH-X ⁵ (IV) (0.5 to 2 mole times the total amount of the monochlorotriazine represented by the formula, the dichlorotriazine (II) and the monochlorotriazine (III)) In the formula, X and X ⁵ are each 2,2,6,6-tetramethyl-4
-Represents a piperidyl group or hydrogen, at least one of which is 2,
Represents a 2,6,6-tetramethyl-4-piperidyl group. ) Is reacted with a diamine represented by the formula (1).
3. The method for producing a polyaminotriazine mixture according to 3. 5. The process according to claim 4, wherein the diamine (IV) wherein X and X ⁵ are 2,2,6,6-tetramethyl-4-piperidyl groups is used. Method. 6. The diamine (IV) according to claim 4, wherein at least 75 mol% of the total of X and X ⁵ is a 2,2,6,6-tetramethyl-4-piperidyl group. Claim 4
The production method described in 1. 7. The method according to claim 4, wherein the base is sodium hydroxide or potassium hydroxide. 8. The method according to claim 4, wherein the organic solvent is at least one selected from xylene and ethylbenzene. 9. The process according to claim 4, wherein the reaction is carried out at 140 to 220 ° C. 10. The method according to claim 4, wherein the reaction is carried out while removing generated water out of the system. 11. The process according to claim 4, wherein the melting point of the polyaminotriazine mixture (I) is in the range of 30 to 110 ° C. 12. A stabilizer for organic materials comprising the polyaminotriazine mixture according to claim 1 as an active ingredient. 13. A method for stabilizing an organic material, wherein the organic material contains the polyaminotriazine mixture according to claim 1. Description: 14. A stabilized organic material comprising the organic material containing the polyaminotriazine mixture according to claim 1.