JP2000154181A - New 2-substituted guanamine compound and flame retardant resin composition containing 2-substituted guanamine compound as active component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having a high nitrogen content, excellent in heat stability and useful as a flame retardant for automobiles, etc., by carrying out a reaction in the presence of a basic catalyst. SOLUTION: The objective compound is represented by formula I to III (X is morpholino, phthalimino or dimethylhydantoinyl; Y is ethylenediamino, piperazinyl, ethyleneurea or the like; Z is ethylenediamino, 1,2-propanediamino, 1,3-propanediamino or the like), e.g. a 1,3-bis[β-(2',4'-diamino-s-triazinyl-6'-) ethyl]ethyleneurea compound represented by formula IV. The above compound is obtained by reacting a cyanoethylated substance prepared by cyanoethylating amines with acrylonitrile with dicyandiamide in the presence of a basic catalyst such as caustic potash.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 2-substituted guanamine compound and a flame-retardant resin composition containing the 2-substituted guanamine compound as an active ingredient.

[0002]

2. Description of the Related Art Flame-retardant resin compositions are widely used for various molded articles, for example, automobiles, electric appliances, OA equipment, office equipment, and the like. Non-halogen-based products are required, and molded products for OA equipment and home appliances are
In many cases, a flame retardant level of V-0 based on the subject 94 of Underwriters Laboratories (UL), which is an American flame retardant standard, or a flame retardancy close to V-0 is required.

A conventionally known flame-retardant resin composition containing a halogen-containing compound and antimony oxide is regarded as a problem because a corrosive or harmful halogen-based gas is generated during combustion or molding. Therefore, a flame-retardant resin composition that does not generate a halogen-based gas at the time of combustion or molding is required, and various flame-retardant resin compositions have been proposed to meet this requirement.

For example, JP-A-53-92855 and JP-A-54
-29350, JP-A-54-77658, JP-A-56-26954
As disclosed in JP-A-57-87462, JP-A-60-110738, etc., hydrous inorganic compounds (for example, magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) are heated. A composition added to a plastic resin and the like are disclosed.

However, according to these compositions, for example, a composition to which magnesium hydroxide is added, it is necessary to use a large amount of a water-containing inorganic compound in order to obtain a high degree of flame retardancy. Not only lowering of the molded article but also deteriorating the physical properties of the obtained molded article.

Further, JP-A-6-87974 and JP-A-6-34077
No. 0 discloses a self-extinguishing polymer composition in which a salt of a specific triazine derivative and an oxygenated acid of phosphorus is mixed with a thermoplastic resin. However, there is a problem that these flame retardants also need to be manufactured through a complicated process, and in order to impart sufficient flame retardancy, the amount of addition must be increased.

As another solution, a method using a substance capable of inducing a foaming action has been proposed. Generally, upon contact with a flame containing a polymer and a plurality of additives, i.e., a phosphorus compound, an impermeable semi-solid glass layer consisting primarily of polyphosphonic acid is formed and the foaming process is controlled. Those intended for activation, those containing nitrogen and acting as foaming agents, and carbon donors for forming an insulating foamed carbon layer (char) between the polymer and the flame containing carbon It has what acts as.

Examples of such effervescent formulations include US Pat. No. 3,810,862 [based on melamine polyphosphate, pentaerythritol and ammonium], US Pat. No. 4,727,102 [melamine cyanurate, Based on hydroxyalkyl derivatives of isocyanuric acid and ammonium polyphosphate], WO 85/05626 [Various compounds of phosphorus and nitrogen, especially melamine phosphate, pentaerythritol polyphosphate and ammonium polyphosphate] Combinations], US Pat. No. 4,50,610 [based on oligomeric derivatives of 1,3,5-triazine and ammonium polyphosphate], EP 14,463 [ammonium polyphosphate, Reaction products of benzylguanamine and aldehydes with various nitrogenated cyclic compounds, That those based on organic compounds selected from the group consisting of benzyl guanamine over formamide copolymer] and the like are known in the.

Also, US Pat. No. 4,201,705 discloses that
A flame-retardant composition using a single-component additive containing both nitrogen and phosphorus in organic molecules has been disclosed.
No. 9870, JP-A-6-25467, JP-A-6-56988, European Patent No. 0475418, etc., it is difficult to use a 1,3,5-triazine derivative polymer or oligomer and ammonium polyphosphate as components. Flammable compositions have been proposed.

[0010] These foamed flame-retardant resins form a porous carbon layer when exposed to a flame, generate less smoke than a system containing a metal compound or a halogenated hydrocarbon, and correspond to polymers. However, they do not always satisfy the flame retardancy required of recent advanced non-halogen flame retardants.

[0011]

SUMMARY OF THE INVENTION The present invention provides a novel 2-
It is an object of the present invention to provide a substituted guanamine compound and to provide a flame-retardant polyolefin-based resin composition by making use of the characteristics of these compounds, which are high in nitrogen content and excellent in thermal stability.

[0012]

The present inventors have found that a novel 2-substituted guanamine compound can be obtained by reacting an amine obtained by cyanoethylating an amine with acrylonitrile and dicyandiamide in the presence of a basic catalyst. It has been discovered that when a 2-substituted guanamine compound synthesized in this way is blended into a thermoplastic resin, the flame retardant in the resin composition decomposes when the resin is burned, and a part of the flame retardant forms vinyl guanamine. It has been found that it reacts with the resin to suppress the lowering of the molecular weight of the resin, and exerts the flame-retardant action of the resin by reducing the heat of combustion due to endotherm during decomposition.
The invention of the flame-retardant resin composition has been completed.

The novel 2-substituted guanamine compound of the present invention is represented by the following formulas (10) to (12).

[0014]

Embedded image In the formula, X represents a morpholino group, a phthalimino group or a dimethylhydantoinyl group.

[0015]

Embedded image In the formula, Y represents an ethylenediamino group, a piperazinyl group, an ethylene urea or a 2-hydroxyethylamino group.

[0016]

Embedded image In the formula, Z is an ethylenediamino group, a 1,2-propanediamino group, a 1,3-propanediamino group, a 1,4-butanediamino group, a 4- (4,6-diamino-triazinylethyl) diethylenetriamino group Represents

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds having an amino group as a raw material of the 2-substituted guanamines in the present invention include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, Diethylenetriamine,
Triethylenetetramine, hexamethylenediamine, ethyleneurea, piperazine, morpholine, dimethylhydantoin, hydantoin, ethanolamine, phthalimide, aniline, o-, m- and p-toluidine, diphenylamine, o-, m- and p-phenylenediamine, m-nitroaniline, 3-nitro-2-methylaniline, ε-caprolactam, carbazole, aminopyridine and the like.

However, among these, compounds that impart high flame retardancy to the composition include ethanolamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4 butanediamine, diethylenetriamine, piperazine, and the like. Ethylene urea, dimethylhydantoin, phthalimide, morpholine and the like. The guanamine substituted at the 2-position in the present invention can be obtained from a cyanoethyl compound obtained by a reaction between an amine and acrylonitrile as a raw material [for example, Journal, Ob, Chemical, Society 1952, p. 1279 (S. Birtwell: JCS , 1952),
And the method described in Comprehensive, Heterocyclic, Chemistry II, Vol. 6, pp. 613] and a reaction of a cyanoethyl compound with dicyandiamide.

The resin in which the compound of the present invention can be used is applicable to all resins and is not particularly limited, but is particularly useful for polyolefin resins.
Examples of the polyolefin resin include low-density polyethylene, high-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene-acrylic acid copolymer, ethylene -Methacrylic acid copolymer and the like. Other applicable resins include, for example, phenolic resins, urea resins, melamine resins, unsaturated polyesters, alkyd resins, thermosetting resins such as epoxy resins, polystyrene, impact-resistant polystyrene, expanded polystyrene, acrylonitrile-styrene copolymers. Acrylonitrile-styrene-butadiene copolymer (AB
S), thermoplastic resins such as polypropylene, petroleum resin, polymethyl methacrylate, polyamide, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, and polycarbonate / ABS mixed resin.

2- to be added to the flame-retardant resin composition of the present invention
The compounding amount of the substituted guanamine compound should be 3 to 70 parts by weight, preferably 5 to 50 parts by weight, of the 2-substituted guanamine compound based on 100 parts by weight of the synthetic resin.

If the amount of the 2-substituted guanamine compound relative to the synthetic resin is less than the above range, the desired flame retardant effect cannot be obtained, and the compound may be added beyond this range.
No further improvement in flame retardancy is observed, so adding it alone will only increase the cost. In the practice of the present invention, the flame retardancy of the resin can be further enhanced by using a 2-substituted guanamine and ammonium polyphosphate in combination. In this case, they should be mixed at a ratio of 1 to 90 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the synthetic resin.

As the ammonium polyphosphate used in the present invention, commercially available ammonium polyphosphate can be used. In addition, type II ammonium polyphosphate fine particles described in JP-A-4-300204, Melamine-coated ammonium polyphosphate described in No. 56988 can also be used. The melamine-coated ammonium polyphosphate is an ammonium polyphosphate in which melamine is added or adhered to the above-mentioned ammonium polyphosphate particle surface.

In the flame-retardant resin composition of the present invention, various additives generally added to the synthetic resin, such as an ultraviolet absorber, a light stabilizer, an antistatic agent, a copper damage inhibitor, a lubricant, Neutralizing agents, inorganic fillers, pigments, peroxides and the like can be used in combination.

The method for producing the resin composition of the present invention is not particularly limited, but a predetermined amount of each of the above-mentioned components is charged into a stirring and mixing apparatus, for example, a Henschel mixer, a super mixer or a tumbler mixer, and mixed by stirring for 1 to 10 minutes. Thereafter, the obtained mixture can be obtained by melt-kneading using a roll kneader or an extruder and pelletizing.

According to the present invention, since the guanamine compound is present in the synthetic resin, non-flammable gases such as water, carbon dioxide, and nitrogen are generated by pyrolysis due to ignition or contact with a flame. It produces carbonaceous residues and exhibits excellent self-extinguishing properties.

[0026]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The evaluation method of flame retardancy in Examples and Comparative Examples was carried out in accordance with the vertical combustion test specified in "Pullability Test of Plastic Materials for Equipment Parts" of UL Subject 94 (Underwriter Laboratories, Inc.). It was done.

Example 1 A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and heating tank was charged with 86 g of ethylene urea and 1.5 g of caustic potassium as a catalyst, and heated and stirred at an internal temperature of 80 ° C. or higher. While acrylonitrile 110g
Was added dropwise over 1 hour, the internal temperature was further maintained at 90 to 110 ° C. for 2 hours, then, after cooling the system, the reaction product was dried under reduced pressure to obtain 192 g of a pale yellow oily intermediate (crude yield 100%). ).

The intermediate obtained in the above reaction was placed in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and heating tank.
2 g, dicyandiamide 18.5 g, caustic potassium 2.0 g, and dimethyl sulfoxide 30 ml were charged and gradually heated. The reaction solution became transparent as the temperature rose, and the reaction progressed rapidly when the temperature reached around 120 ° C. The internal temperature was controlled at 130 to 150 ° C. while cooling as appropriate, and heating and stirring were continued for 5 hours. After the reaction mixture was concentrated under reduced pressure, 100 ml of water was poured, the precipitated pale yellow precipitate was collected by filtration, washed with 100 ml of water, and the obtained powdery solid was dried under reduced pressure. From the results of NMR and MS analysis, this compound was found to be 1,3-bis [β-
(2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] ethylene urea [65.8 g (70.4% yield)].

The compound of the present invention, 1,3-bis [β- (2 ′, 4′-
The structural formula and physical properties of the diamino-S-triazinyl-6 ′-) ethyl] ethylene urea compound are as follows.

[0030]

Embedded image

Pale yellow crystal, melting point 218 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 2.81 (t, 4H, J = 6 Hz), 3.46 (s, 4H), 3.52
(t, 4H, J = 6Hz) Mass: (FAB +) 361 (M ⁺⁺ 1)

Example 2 A flask was charged with 86.3 g of piperazine hexahydrate in the same manner as in Example 1, and the internal temperature was set to 80 ° C.
While heating the mixture, 55.65 g of acrylonitrile was added dropwise over 1.5 hours.Then, the mixture was heated at an internal temperature of 95 to 100 ° C. for 4 hours.After cooling the system, the reaction product was dried under reduced pressure to give a pale yellow crystalline intermediate. 86.63 g of the compound (crude yield 100%) was obtained.

43.0 g of the intermediate obtained in the above reaction, 2.6 g of potassium hydroxide and 100 ml of dimethyl sulfoxide were heated to a temperature of 140 ° C., and 50.0 g of dicyandiamide was dividedly administered, and the internal temperature was lowered to 120 to 140 ° C. while cooling appropriately. Control and heating and stirring were continued for 3 hours. After concentrating the reaction mixture under reduced pressure, 200m
1 l of water was poured, and the precipitated pale yellow precipitate was collected by filtration, washed with 100 ml of water, and dried under reduced pressure to obtain a powdery solid. NMR and M
From the result of S analysis, this compound was found to be 1,4-bis [β-
(2 ', 4'-Diamino-S-triazinyl-6'-) ethyl]
It was confirmed to be piperazine [yield: 68.7 g (yield: 85.0%)].

The compound of the present invention, 1,4-bis [β- (2 ′,
The structural formula and physical properties of the 4′-diamino-S-triazinyl-6 ′-) ethyl] piperazine compound are as follows.

[0035]

Embedded image

Pale yellow crystal, melting point: 238 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 2.93 (t, 4H, J = 7 Hz), 3.16 (t, 2H, J = 7H)
z), 3.26 (t, 2H, J = 7Hz), 3.56 (m, 4H) Mass: (FAB +) 361 (M ⁺⁺ 1)

[Example 3] In the same manner as in Example 1, 87.1 g of morpholine was charged into a flask, and while heating the internal temperature to 100 ° C, 58.4 g of acrylonitrile was added dropwise over 3 hours. After heating at 125 ° C. for 1 hour and cooling the system, the reaction product was dried under reduced pressure to obtain 139.4 g (crude yield 99.5%) of a yellow transparent oily intermediate.

123.0 g of the intermediate obtained in the above reaction, 73.7 g of dicyandiamide, 4.9 g of potassium hydroxide and 100 ml of dimethyl sulfoxide were mixed, heated at 130 ° C. with stirring for 4 hours, and 50 ml of methanol was added to the system. The product was collected by filtration and washed with 100 ml of methanol and 100 ml of water.
Drying gave a pale yellow-green powdery solid. NMR and MS
As a result of the analysis, this compound was identified as 4- [β- (2 ′, 4′-
Diamino-S-triazinyl-6 ′-) ethyl] morpholine [yield: 141.3 g (yield: 72.05%)].

The structural formula and physical properties of the 4- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] morpholine compound of the present invention are as follows.

[0040]

Embedded image

Pale yellow crystal, melting point 240-243 ° C., weakly basic ¹ H-NMR (CD ₃ COOD); δ 3.33 (t, 2H, J = 5 Hz), 3.42 (s, 4H), 3.56
(s, 4H), 3.94 ( t, 2H, J = 5Hz) 13 C-NMR (CD 3 COOD); δ44.60 (1C), 52.91 (1C), 54.49 (2C), 6
4.84 (2C), 165.06 (2C), 173.73 (1C) Mass: (FAB +) 225 (M ⁺⁺ 1)

Example 4 In the same manner as in Example 1, 60 g of ethylenediamine was charged into a flask, and 110 g of acrylonitrile was added dropwise over 1 hour while heating the internal temperature to 80 ° C. or higher. After heating for 1 hour and then cooling the system, the reaction product was evaporated to dryness under reduced pressure to obtain 166 g of a pale yellow transparent oily intermediate (crude yield 100%).

16.6 g of the intermediate obtained in the above reaction, 20.0 g of dicyandiamide and 2.8 g of caustic potassium were mixed in 40 ml of dimethyl sulfoxide, heated at 130 ° C. with stirring for 5 hours, and then the reaction mixture was removed under reduced pressure. This was washed with 100 ml of water, a pale yellow precipitate was collected by filtration, and further washed with water 1
After washing with 00 ml and drying, a powdery solid was obtained. NMR and M
From the result of S analysis, this compound was found to be N, N'-bis [β-
(2 ', 4'-Diamino-S-triazinyl-6'-) ethyl]
It was confirmed to be ethylenediamine [26.2 g (yield 78.3%)].

The N, N'-bis [β-
(2 ', 4'-Diamino-S-triazinyl-6'-) ethyl]
The structural formula and physical properties of the ethylenediamine compound are as shown below.

[0045]

Embedded image

Pale yellow crystal, melting point 270 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 3.53 (s, 4H), 3.71 (s, 4H), 4.41 (s, 4
H), ¹³ C-NMR (CD ₃ COOD); δ 44.88 (2 C), 45.71 (2 C), 62.36 (2 C), 1
64.79 (4C), 165.00 (2C)

Example 5 As in Example 1, 73.57 g of phthalimide, 9.27 g of tributylamine and 50 ml of dimethyl sulfoxide were charged into a flask, the internal temperature was heated to 140 ° C., and 37.15 g of acrylonitrile was added over 1 hour. After dropwise addition, the mixture was heated at an internal temperature of 130 ° C. for 1 hour, and then dried under reduced pressure. To this, 100 ml of water was added, and the precipitate was filtered under reduced pressure. The crystals were washed with methanol and dried to obtain a white crystalline intermediate.
88.3 g (crude yield 88.2%) was obtained.

20.0 g of the intermediate obtained in the above reaction, 12.6 g of dicyandiamide and 1.7 g of potassium hydroxide were mixed in 10 ml of dimethyl sulfoxide, and the mixture was heated with stirring at 140 ° C. for 2.5 hours, and 50 ml of water was added to the reaction mixture. And cooled to room temperature, and the pale yellow precipitate was collected by filtration, washed with water and dried to obtain a yellow powdery solid. From the results of NMR and MS analysis,
This compound was N- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] phthalimide [yield 17.68 g (yield
62.2%)].

The structural formula and physical properties of the N- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] phthalimide compound of the compound of the present invention are as follows.

[0050]

Embedded image

White crystal, melting point 268-271 ° C., weakly basic ¹ H-NMR (CD ₃ COOD); δ 2.63 (t, 2 H, J = 12 Hz), 3.88 (t, 2 H, J = 12
Hz), 6.61-6.73 (m, 4H) ¹³ C-NMR (CD ₃ COOD); δ 35.79 (1 C), 36.45 (1 C), 122.90 (2 C),
131.56 (2C), 134.25 (2C), 166.83 (2C), 167.60 (1C), 174.50
(2C) Mass: (FAB +) 284 (M ⁺ )

Example 6 In the same manner as in Example 1, 128 g of dimethylhydantoin and 10 g of tributylamine were added to a flask.
g, 500 ml of water and 165 g of acrylonitrile were heated and refluxed for 4 hours at an internal temperature of 80 ° C., and the reaction mixture was evaporated to dryness under reduced pressure to obtain 265.9 g of a pale yellow crystalline intermediate (crude yield 97.8 g).
%).

18.1 g of the intermediate obtained in the above reaction, 10.1 g of dicyandiamide, and 0.56 g of potassium hydroxide are mixed in 20 ml of diethylene glycol dimethyl ether, and the mixture is gradually heated with stirring and controlled at an internal temperature of 120 to 140 ° C. for 6 hours. After heating, the reaction mixture was concentrated under reduced pressure, and then added to water.
100 ml was added and the precipitated pale yellow precipitate was collected by filtration, washed with water and dried to obtain a yellow powdery solid. From the results of NMR and MS analysis, this compound was found to be 3- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] 5,5-dimethylhydantoin [18.0 g (73.1% yield) )].

The structural formula and physical properties of the 3- [β- (2 ', 4'-diamino-S-triazinyl-6'-) ethyl] 5,5-dimethylhydantoin compound of the present invention are as follows. .

[0055]

Embedded image

Yellow crystals, melting point: 270 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 1.20 (s, 6H, J = 6 Hz), 2.75 (t, 2H, J = 6H)
z), 3.73 (t, 2H, J = 6Hz) Mass: (FAB +) 266 (M ⁺⁺ 1)

Example 7 In the same manner as in Example 1, 30.5 g of ethanolamine was charged into a flask, and while maintaining the internal temperature at 130 ° C. or higher, 74.3 g of acrylonitrile was added dropwise thereto. After heating and stirring, the reaction mixture was evaporated to dryness under reduced pressure to obtain 86.7 g (99% crude yield) of an orange oily intermediate.

8.36 g of the intermediate obtained in the above reaction, 10.5 g of dicyandiamide and 0.84 g of potassium hydroxide were added to methyl cellosolve 42.
After stirring for 3 hours at an internal temperature of 140 ° C., the reaction mixture was evaporated to dryness under reduced pressure.
Water was added thereto, and the precipitate was collected by filtration and dried to obtain a pale yellow powdery solid. From the results of NMR and MS analysis, this compound was found to be N, N-bis [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] aminoethanol [yield 12.8 g
(76% yield)].

The N, N-bis [β- (2 ′,
The structural formula and physical properties of the 4'-diamino-S-triazinyl-6 '-) ethyl] aminoethanol compound are as follows.

[0060]

Embedded image

Pale yellow crystal, melting point> 300 ° C., weakly basic ¹ H-NMR (CD ₃ COOD); δ3.35 (t, 2H, J = 1.5 Hz), 3.53 (s, 4H), 3.
98 (t, 2H, J = 1.5Hz), 4.41 (s, 4H) 13 C-NMR (CD 3 COOD); δ45.07 (1C), 50.12 (2C), 57.83 (2C), 6
2.37 (1C), 164.80 (2C), 164.92 (2C), 174.45 (1C), 174.60 (1
C)

Example 8 In the same manner as in Example 1, 60 g of ethylenediamine and 500 ml of water were charged into a flask, 265 g of acrylonitrile was added dropwise thereto, and the mixture was heated under reflux at an internal temperature of 80 ° C. for 4 hours. The mixture was evaporated to dryness under reduced pressure to obtain 265.9 g of a pale yellow crystalline intermediate (crude yield: 97.8%).

13.6 g of the intermediate obtained in the above reaction, 21.5 g of dicyandiamide and 2.0 g of caustic potash were mixed in 20 ml of dimethyl sulfoxide, and the temperature was gradually increased while stirring and the internal temperature was adjusted to 120 ° C.
After heating and stirring at ℃ 140 ° C. for 3 hours, the mixture was kept at this temperature for 5 hours, added with 200 ml of water, cooled to room temperature, and the precipitate was collected by filtration, washed with water and dried to obtain a pale yellow powdery solid. NM
From the results of R and MS analysis, this compound was found to be tetrakis [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] ethylenediamine [yield 29.2 g (95% yield)]. confirmed.

The compound of the present invention, tetrakis [β- (2 ′,
The structural formula and physical properties of the 4'-diamino-S-triazinyl-6 '-) ethyl] ethylenediamine compound are as follows.

[0065]

Embedded image

Yellow crystal, melting point 270 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 3.42 (s, 4H), 3.53 (s, 8H), 3.68 (s, 8
H), ¹³ C-NMR (CD ₃ COOD); δ 44.76 (4 C), 45.66 (4 C), 49.83 (2 C), 1
65.09 (8C), 174.31 (4C)

Example 9 A flask was charged with 10.3 g of diethylenetriamine and 50 ml of water in the same manner as in Example 1.
31.8 g of acrylonitrile was added dropwise to this, and the internal temperature was further increased to 80.
After heating under reflux at a temperature of 4 ° C. for 4 hours, the reaction mixture was evaporated to dryness under reduced pressure to obtain 38.8 g (100% crude yield) of a pale yellow crystalline intermediate.

5.0 g of the intermediate obtained in the above reaction, 6.85 g of dicyandiamide, and 1.0 g of potassium hydroxide were mixed with dimethyl sulfoxide 1
And the temperature was gradually increased with stirring, the internal temperature was controlled at 140 ° C., and heating and stirring were continued for 5 hours.
0 ml was added and the mixture was cooled to room temperature, and the precipitate was collected by filtration, washed with water and dried, and yellow powdery solid pentakis [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] diethylenetriamine [yield] 6.43 g (60% yield)].

The compound of the present invention, pentakis [β- (2 ′,
The structural formula and physical properties of the 4'-diamino-S-triazinyl-6 '-) ethyl] diethylenetriamine compound are as follows.

[0070]

Embedded image

Yellow crystals, melting point 260 ° C. (decomposition), weakly basic

Example 10 In the same manner as in Example 1, 14.8 g of 1,3-propanediamine and 100 ml of water were charged into a flask, and 53.1 g of acrylonitrile was added dropwise thereto. After heating under reflux for an hour, the reaction mixture was evaporated to dryness under reduced pressure to obtain 55.9 g (crude yield 97.6%) of a pale yellow oily intermediate.

12.0 g of the intermediate obtained in the above reaction, 17.6 g of dicyandiamide, and 1.0 g of caustic potash were mixed in 30 ml of dimethyl sulfoxide, and the temperature was gradually raised while stirring, and the internal temperature was increased to 140 g.
The resulting mixture was cooled to room temperature by adding 200 ml of water, and the precipitate was collected by filtration, washed with water and dried to obtain a yellow powdery solid. From the results of NMR and MS analysis, this compound was found to be tetrakis [β- (2 ′, 4′-
Diamino-S-triazinyl-6 ′-) ethyl] 1,3 propanediamine [18.96 g (72.7% yield)].

The compound of the present invention, tetrakis [β- (2 ′,
4'-Diamino-S-triazinyl-6 '-) ethyl] 1,3
The structural formula and physical properties of the propanediamine compound are as follows.

[0075]

Embedded image

Yellow crystals, melting point 255 ° C. (decomposition), weakly basic ¹ H-NMR (CD ₃ COOD); δ 2.35 (quint, 2H), 3.33 (t, 4H, J = 7.7 H)
z), 3.51 (s, 8H), 4.41 (s, 8H) ¹³ C-NMR (CD ₃ COOD); δ 23.70 (1 C), 45.21 (2 C), 45.78 (4 C), 6
2.32 (4C), 164.67 (4C), 164.86 (4C), 173.21 (1C), 174.02 (1
C), 174.35 (1C), 178.38 (1C)

Example 11 In the same manner as in Example 1, 25.0 g of 1,4-butanediamine and 150 ml of water were charged into a flask, and 63.6 g of acrylonitrile was added dropwise thereto. After heating under reflux for an hour, the reaction mixture was evaporated to dryness under reduced pressure to give 84.0 g of a pale yellow crystalline intermediate (crude yield 100
%).

12.0 g of the intermediate obtained in the above reaction, 16.8 g of dicyandiamide, and 1.0 g of caustic potash were mixed in 15 ml of dimethyl sulfoxide, and the temperature was gradually raised while stirring, and the internal temperature was increased to 140 g.
The mixture was heated and stirred for 8 hours while controlling the temperature to 145 ° C., 200 ml of water was added to the reaction mixture, and the mixture was cooled to room temperature. The precipitate was collected by filtration, washed with water, and dried to obtain tetrakis [β-
(2 ', 4'-Diamino-S-triazinyl-6'-) ethyl]
1,4-butanediamine [16.45 g (64.8% yield)]
I got

The structural formula and physical properties of [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] 1,4-butanediamine compound of the present invention are as follows.

[0080]

Embedded image

Yellow crystals, melting point: 217 ° C. (decomposition), weakly basic

Example 12 In the same manner as in Example 1, a flask was charged with 7.4 g of 1,2-propanediamine and 50 ml of water, and 26.5 g of acrylonitrile was added dropwise thereto. After heating and refluxing for 2 hours, the reaction mixture was evaporated to dryness under reduced pressure, and 21.7 g of a pale yellow crystalline intermediate (crude yield 75.
9%).

14.3 g of the intermediate obtained in the above reaction, 21.5 g of dicyandiamide and 2.0 g of caustic potassium were mixed in 20 ml of dimethyl sulfoxide, and the temperature was gradually increased while stirring, and the internal temperature was adjusted to 120 ° C.
After heating and stirring at 4 ° C. for 4 hours, the reaction mixture was concentrated under reduced pressure, 100 ml of water was added thereto, and the mixture was cooled to room temperature. The precipitate was collected by filtration, washed with water and dried to give a yellow powdery solid. Tetrakis [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] 1,2-propanediamine [yield 15.
9 g (yield 51%)].

The compound of the present invention, tetrakis [β- (2 ′,
4'-Diamino-S-triazinyl-6 '-) ethyl] 1,2
-The structural formula and physical properties of the propanediamine compound are as follows.

[0085]

Embedded image

Yellow crystals, melting point 220 ° C. (decomposition), weakly basic

Example 13 The guanamine compound obtained in Examples 1 to 12 was used alone or in combination with a polypropylene resin [trade name: Flowbrene B200, manufactured by Sumitomo Seika] or ammonium polyphosphate [trade name: Terage C60, manufactured by Chisso] in the proportions shown in Table 1,
After mixing using a tumbler blender, the mixture is melt-kneaded at a temperature of 200 ° C. and extruded from an extruder having a diameter of 30 mm to form a pellet-shaped resin composition. , A 1/16 inch thick test piece was prepared, and its flame retardancy was examined in accordance with the vertical combustion test specified in UL Subject 94. The test results are shown in Table 1. It was as shown.

[Comparative Example 1] Melamine cyanurate and ammonium polyphosphate (same as in Example 13) were blended with a polypropylene resin (same as in Example 13) in the ratio shown in Table 1, and a tumbler blender was used. After mixing, the mixture was melt-kneaded at a temperature of 200 ° C. and extruded from an extruder having a caliber of 30 mm to obtain a pellet-shaped resin composition, which was processed by an injection molding machine [cylinder temperature 220 ° C., mold temperature 60 ° C.] , A 1/16 inch thick test piece was prepared,
When examined in accordance with the vertical combustion test specified in L Subject 94, the test results were as shown in Table 1.

Comparative Example 2 Only ammonium polyphosphate (same as in Example 13) was blended with a polypropylene resin (same as in Example 13) at the ratio shown in Table 1, and mixed using a tumbler blender. Thereafter, the mixture is melt-kneaded at a temperature of 200 ° C., extruded from an extruder having a diameter of 30 mm into a pellet-shaped resin composition, and processed by an injection molding machine [cylinder temperature 220 ° C., mold temperature 60 ° C.] A 1/16 inch test piece was prepared and its flame retardancy was evaluated as UL Subject 94.
The results of these tests were as shown in Table 1 when examined in accordance with the vertical combustion test specified in Table 1.

[0090]

[Table 1]

[Example 14] Nylon resin [Product name: N]
-6, Novamid-1020, manufactured by Mitsubishi Engineering Plastics] 100
N, N′-bis [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] ethylenediamine was blended in a ratio of 30 parts by weight with respect to parts by weight. When treated in the same manner and the flammability was examined, the test result of the flame retardancy showed V-0.

Example 15 Polyphenylene ether resin [trade name: Noryl 115-7001, manufactured by GE Japan]
N, N'-bis [β- (2 ', 4'
-Diamino-S-triazinyl-6 ′-) ethyl] ethylenediamine in a ratio of 10 parts by weight and ammonium polyphosphate in a ratio of 30 parts by weight, and treated in the same manner as described above. The test result of sex was V-1.

Example 16 ABS resin [trade name: K-
3272, manufactured by Sumitomo Dow]
[Β- (2 ′, 4′-Diamino-S-triazinyl-6 ′-) ethyl] 17 parts by weight of 5,5-dimethylhydantoin and 50 parts by weight of ammonium polyphosphate are blended and treated in the same manner as described above. Then, when the flame retardancy was examined, the test result of the combustibility was V-0.

[Example 17] Polycarbonate resin [trade name: Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics] 8
For 0 parts by weight and 20 parts by weight of the ABS resin [same as in Example 16], 3- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] 5,5-dimethylhydantoin 1
When 5 parts by weight and 45 parts by weight of ammonium polyphosphate were blended and treated in the same manner as in the above embodiment, and the flame retardancy was examined, the test result of the flammability was V-0.

[Example 18] Polycarbonate resin [Product name: Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics] 8
For 0 parts by weight and 20 parts by weight of the ABS resin [same as in Example 16], 3- [β- (2 ′, 4′-diamino-S-triazinyl-6 ′-) ethyl] 5,5-dimethylhydantoin 3
When 0 part by weight was blended and treated in the same manner as described above, and the flame retardancy was examined, the test result of flammability showed V-2.

Example 19 100 parts by weight of a polybutylene terephthalate resin (trade name: Planac BT-1000, manufactured by Dainippon Ink) was used to prepare 3- [β- (2 ′, 4 ′).
-Diamino-S-triazinyl-6 '-) ethyl], 20 parts by weight of 5,5-dimethylhydantoin and 30 parts by weight of ammonium polyphosphate were blended and treated in the same manner as in the above-mentioned embodiment, and the flame retardancy was examined. However, the test result of flammability is V
-0 was indicated.

[0097]

The compound of the present invention is useful as a flame retardant, a heat resistance modifier, a resin curing agent, and the like. By using these specific 2-substituted guanamine compounds as the flame retardant, a halogen-based flame retardant can be used. Without this, the flame retardancy of the thermoplastic resin can be dramatically increased.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) C08L 101/00 C08L 101/00 C09K 21/04 C09K 21/04 21/10 21/10 F-term (reference) 4C063 AA01 BB03 CC54 DD07 DD23 DD43 EE10 4H028 AA30 BA06 4J002 BA01 BB031 BB051 BB061 BB081 BB121 BB151 BC031 BC061 BG051 BG101 BN141 BN151 CB001 CC031 CC161 CC181 CD001 CF011 CF061 CG1 CF071

Claims (3)

[Claims] 1. A novel 2-substituted guanamine compound represented by the general formulas (1) to (3). Embedded image In the formula, X represents a morpholino group, a phthalimino group or a dimethylhydantoinyl group. Embedded image In the formula, Y represents an ethylenediamino group, a piperazinyl group, an ethyleneurea group, or a 2-hydroxyethylamino group. Embedded image In the formula, Z is an ethylenediamino group, a 1,2-propanediamino group, a 1,3-propanediamino group, a 1,4-butanediamino group, a 4- (4,6-diamino-triazinylethyl) diethylenetriamino group Represents 2. A flame-retardant resin composition comprising, as an active ingredient, a 2-substituted guanamine compound represented by the general formulas (4) to (6). Embedded image In the formula, X represents a morpholino group, a phthalimino group or a dimethylhydantoinyl group. Embedded image In the formula, Y represents an ethylenediamino group, a piperazinyl group, an ethyleneurea group, or a 2-hydroxyethylamino group. Embedded image In the formula, Z is an ethylenediamino group, a 1,2-propanediamino group, a 1,3-propanediamino group, a 1,4-butanediamino group, a 4- (4,6-diamino-triazinylethyl) diethylenetriamino group Represents 3. A flame-retardant resin composition comprising, as active ingredients, a 2-substituted guanamine compound represented by the general formulas 7 to 9 and ammonium polyphosphate. Embedded image In the formula, X represents a morpholino group, a phthalimino group or a dimethylhydantoinyl group. Embedded image In the formula, Y represents an ethylenediamino group, a piperazinyl group, an ethyleneurea group, or a 2-hydroxyethylamino group. Embedded image In the formula, Z is an ethylenediamino group, a 1,2-propanediamino group, a 1,3-propanediamino group, a 1,4-butanediamino group, a 4- (4,6-diamino-triazinylethyl) diethylenetriamino group Represents