JPH09255693A - Ethylenediamine-phenylphosphonic acid salt, its production and flame-retardant resin composition compounded with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To quantitatively obtain the subject new compound salt not generating smoke and a toxic gas on processing and combustion and useful as a flame retartant for resins, etc., by dropwisely adding an aqueous ethylenediamine solution to an aqueous phenylphosphonic acid solution and subsequently cooling the reaction solution to room temperature. SOLUTION: This new ethylenediamine-phenylphosphonic acid salt comprises 1 mole of ethylenediamine and 2 moles of phenylphosphonic acid. The compound salt is excellent in flame retardancy, water resistance and heat resistance, does not generate smoke and a toxic gas on processing and combustion, and is useful as a flame retardant for compounding with resins, etc. The compound salt is obtained by dropwisely adding an aqueous ethylenediamine solution having a concentration of 10-70% to an aqueous phenylphosphonic acid solution heated to 40-100 deg.C and having a concentration of 5-40%. Therein, the phenylphosphonic acid and the ethylenediamine are preferably reacted with each other in a molar ration of 1:(0.45-0.55).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amine-phosphonate, a process for producing the same, and flame retardation of a resin using the same.

[0002]

2. Description of the Related Art Conventionally, halogen-based flame retardants have been widely used because of their excellent flame retardancy, resin physical properties, and price against flame retardation of resins. In addition, the generation of toxic gas during combustion has come to be regarded as a problem, and in recent years, a shift to a method of achieving flame retardance without using a halogen-based compound is progressing.

Examples of non-halogen flame retardants include metal hydroxides such as magnesium hydroxide and aluminum hydroxide, nitrogen compounds such as isocyanuric acid and melamine, phosphorus compounds such as red phosphorus, triphenyl phosphate, and phosphoric acid ester oligomers. It has been known. Regarding phenylphosphonic acid, which is a phosphorus-based compound, Japanese Patent Publication No. 7-9888
Application as a flame retardant has been reported in Japanese Patent Publication No. 2 and the like.

Further, ammonium polyphosphate and several kinds of organic amine-phosphate salts are disclosed in literatures, patent publications and the like as non-halogen flame retardants containing nitrogen and phosphorus. Examples of the organic amine-phosphate include ethylenediamine-phosphate (for example, JP-A-5-15611).
6), melamine-phosphate (for example, JP-A-7-
No. 258479), an amino-S-triazine salt of bis- (pentaerythritol phosphate) phosphoric acid (Japanese Patent Publication No. 21679/1992), and the like.

[0005]

Generally, phosphorus- and nitrogen-containing salt-type flame retardants have high flame retardancy and can be easily produced, but many of them have drawbacks in water resistance and heat resistance. There's a problem. On the other hand, regarding phenylphosphonic acid, although it has flame retardant performance, its water resistance is extremely low,
Regarding the heat resistance, there is also a problem that the weight is reduced from around 200 ° C. according to thermal analysis.

The present invention has been made in view of the above problems, and an object thereof is to have excellent flame retardancy, water resistance and heat resistance,
It is intended to provide an ethylenediamine-phosphonate that is easy to produce, a method for producing the same, and a flame-retardant resin composition containing the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems. As a result, by using phenylphosphonic acid as a salt of ethylenediamine, heat resistance and water resistance are compared to phenylphosphonic acid. However, the present invention was completed and the present invention was completed, and the present invention was completed.

That is, the present invention relates to ethylenediamine-phenylphosphonate, a method for producing the same, and a flame-retardant resin composition containing the same as a flame retardant in a resin.

Hereinafter, the present invention will be described in detail.

The ethylenediamine-phenylphosphonate of the present invention comprises 1 mol of ethylenediamine and 2 mol of phenylphosphonic acid, and is a white scale-like crystal having a melting point of 288 to 293 ° C.

The result of elemental analysis is C 44.6%, H
5.8%, N 7.4%, P 16.9% (theoretical value C
44.7%, H 5.8%, N 7.4%, P 1
It was 6.5%).

The infrared spectrum, thermobalance measurement and crystal structure analysis results are as follows.

The infrared spectrum is 3 as shown in FIG.
430, 3100 to 2600, 2215, 1654, 1
556, 1482, 1437, 1370, 1230, 1
144, 1085, 1041, 1020, 996, 92
9, 834, 796, 752, 717, 699, 56
It has absorption peaks at 2, 529 and 506 (cm ^-1 ).

The results of thermobalance measurement under the heating rate condition of 20 ° C./min were 1% weight loss temperature 325 ° C., 5% weight loss temperature 344 ° C., 10% weight loss temperature 363 ° C., and 50% weight loss temperature 433 ° C. .

As a result of X-ray crystal structure analysis, (2θ angle) 1
It had peaks of scattering angles at 0.7, 16.0, 21.5, 32.4, and 37.9.

The ethylenediamine-phenylphosphonate of the present invention is produced by dropping an ethylenediamine aqueous solution into a phenylphosphonic acid aqueous solution heated to 40 to 100 ° C. When the temperature is lower than 40 ° C, phenylphosphonic acid is not completely dissolved, and when the temperature is higher than 100 ° C, the reaction solution and the produced salt may be colored. After the dropping is completed, the reaction solution is cooled to room temperature to quantitatively obtain a salt.

The concentration of the aqueous phenylphosphonic acid solution during the production of ethylenediamine-phenylphosphonate is 5-40.
% Is preferable, and 10 to 30% is particularly preferable. If it is less than 5%, the production efficiency may be reduced and the produced salt may be dissolved in the reaction solution. On the other hand, if it exceeds 40%, the viscosity of the system at the time of salt formation increases and stirring becomes difficult, and it may be difficult to completely dissolve the starting phenylphosphonic acid in the aqueous solution.

The concentration of the ethylenediamine aqueous solution is 10 to 7
0% is preferred. If it is less than 10%, the production efficiency is lowered, and further the produced salt may be dissolved in the reaction solution. On the other hand, 70
When the content exceeds 100%, when added dropwise to the phenylphosphonic acid aqueous solution,
In addition to the heat of formation of the salt, heat of dissolution is generated, which makes it difficult to control the reaction temperature, and further, it may be difficult to stir the reaction solution due to an increase in the concentration of the reaction solution.

The amounts of phenylphosphonic acid and ethylenediamine to be dropped at the time of charging are preferably in the range of 0.45 to 0.55 molar ratio of ethylenediamine to 1 mol of phenylphosphonic acid, and particularly preferably 0.50 molar ratio. In the case of excess ethylenediamine, the once precipitated ethylenediamine-phenylphosphonate salt is redissolved and the yield is reduced, and the amine remains in the salt after filtration and drying, which causes coloring when used as a flame retardant. In the case of excess phenylphosphonic acid, when cooled to room temperature after completion of the reaction, unreacted phenylphosphonic acid also precipitates at the same time and the crystal purity decreases, and the reaction solution is biased to the acidic side and the salt is easily dissolved, resulting in a high yield. It may decrease.

There is no particular limitation on the dropping rate of ethylenediamine, as long as the reaction temperature can be controlled with respect to the heat of salt formation.

The salt precipitated from the aqueous solution is taken out by a filtration operation, and the water is evaporated by drying to obtain the intended product, ethylenediamine-phenylphosphonate.

The ethylenediamine-phenylphosphonate of the present invention, which is composed of 1 mol of ethylenediamine and 2 mol of phenylphosphonic acid, is useful as a flame retardant and is particularly excellent in heat resistance with a 1% weight loss temperature of 300 ° C. or higher. Can be used.

Examples of usable resins include thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester, alkyd resin, and epoxy resin,
Low density polyethylene, high density polyethylene, ethylene-
Vinyl acetate copolymer, polystyrene, high impact polystyrene, expanded polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer (ABS), polypropylene, petroleum resin,
Polymethylmethacrylate, polyamide, polycarbonate, polyacetal, polyethylene terephthalate,
Examples thereof include thermoplastic resins such as polybutylene terephthalate, polyphenylene ether, and polycarbonate / ABS mixed resin.

The amount of the ethylenediamine-phenylphosphonate of the present invention to be blended in the resin varies depending on the type of the blended resin and the desired flame retardant performance, but is in the range of 1 to 150 parts by weight per 100 parts by weight of the resin. Good to add.

If desired, the resin composition containing ethylenediamine-phenylphosphonate of the present invention may further contain 1 to 100 parts by weight of another flame retardant such as ammonium polyphosphate. Further, a benzotriazole-based UV absorber, a light stabilizer such as a 2,2,6,6-tetramethylpiperidine derivative, and a hindered phenol-based antioxidant are added in an amount of 0.05 to 5% by weight, respectively. Is also good.
In addition, an antistatic agent or an inorganic filler such as talc may be added if necessary.

As a method of blending the ethylenediamine-phenylphosphonate of the present invention with a resin, when blending with a thermosetting resin, it is dispersed in a resin raw material in advance and then cured. In the case of blending with a thermoplastic resin, for example, a conical blender, a tumbler mixer, etc. may be mixed with necessary blending reagents, and pelletized with a twin-screw extruder or the like. The method for processing the resin composition thus obtained is not particularly limited, and for example, extrusion molding, injection molding and the like can be performed to obtain the desired molded article.

[0027]

Industrial Applicability The ethylenediamine-phenylphosphonate of the present invention has good heat resistance and water resistance and is useful as a flame retardant. The resin composition containing ethylenediamine-phenylphosphonate exhibits excellent flame retardancy, and has good heat resistance and water resistance.

[0028]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the examples.

Example 1 2 l of 4 equipped with stirrer, thermometer, cooling tube, dropping funnel
In a one-necked flask, 290.4 g of phenylphosphonic acid
(1.80 mol) and 840 g of distilled water were charged and the temperature was raised to 60 ° C. with stirring to completely dissolve phenylphosphonic acid. Then, 55.1 g of ethylenediamine (0.90
30% aqueous solution containing (mol) was added dropwise from the dropping funnel over 1 hour. After completion of dropping, heating of the reaction liquid was stopped while continuing stirring, and the mixture was naturally cooled to room temperature. After 2 hours from the end of dropping, the stirring was stopped and the reaction solution containing salt was filtered,
By drying at 90 ° C. for 4 hours, the target product, ethylenediamine-phenylphosphonate, was obtained almost quantitatively (yield 331.0 g, yield 97.8%).

The evaluation as a flame-retardant resin composition was carried out by the following method.

(Combustion Test) The measurement of the oxygen index according to JIS-K-7201 and the UL combustion test according to the UL94V vertical flammability test were performed.

(Fluidity during processing) JIS-K-7210
The melt flow rate when a load of 2.16 kg was applied at 230 ° C. was measured in accordance with the above.

(Measurement of Resin Density) JIS-K-7112
The measurement was carried out by an underwater substitution method in conformity with.

(Water resistance) The dissolution rate of the flame retardant when a 0.5 × 1.5 × 0.125 inch (about 1.7 g) test piece was immersed in 100 ml of hot water at 70 ° C. for 2 days was measured. It was evaluated by measuring.

(Heat resistant coloration) A test piece was tested at 240 ° C. and 28
Observe the colored state when heated at 0 ° C for 10 minutes.

(Example of Use of Ethylenediamine-Phenylphosphonate as a Flame Retardant) Example 2 The ethylenediamine-phenylphosphonate obtained by the method of Example 1 was converted into polypropylene (703 from Tosoh Corporation).
0B) 60 parts by weight per 100 parts by weight, 180
Roll kneading was performed at ℃. The resin composition obtained by the roll kneading was press-molded at 190 ° C. and 120 kg / cm 2 for 4 minutes, and various test pieces for evaluation were obtained from this and measured and evaluated. Table 1 shows the results.

[0037]

[Table 1]

Example 3 Various test pieces for evaluation were obtained and evaluated by the same method as in Use Example 1 except that 45 parts by weight of ethylenediamine-phenylphosphonate was used. The results are shown in Table 1.

Comparative Examples 1 to 3 Phenylphosphonic acid (KOLON In
DURETIES HIRETAR204), Comparative Example 2 ammonium polyphosphate (Hoechst Exolit 462), Comparative Example 3 ethylenediamine phosphate (Albright & Wilson Amgar)
Table 1 also shows the results of various tests when dNK) was mixed with polypropylene.

[Brief description of drawings]

FIG. 1 is an infrared spectrum diagram of ethylenediamine-phenylphosphonate of the present invention.

Claims (7)

[Claims] 1. An ethylenediamine-phenylphosphonate. 2. The ethylenediamine-phenylphosphonate according to claim 1, which comprises 1 mol of ethylenediamine and 2 mol of phenylphosphonic acid. 3. The ethylenediamine-containing compound according to claim 1 or 2, wherein the ethylenediamine aqueous solution is added dropwise to the phenylphosphonic acid aqueous solution, and after completion of the addition, the reaction solution is cooled to room temperature to quantitatively obtain a salt. Method for producing phenylphosphonate. 4. The method according to claim 3, wherein the ethylenediamine aqueous solution is added dropwise to the phenylphosphonic acid aqueous solution heated to 40 to 100 ° C. 5. The production method according to claim 3, wherein an aqueous solution of ethylenediamine having a solution concentration of 10 to 70% is added dropwise to an aqueous solution of phenylphosphonic acid having a solution concentration of 5 to 40%. 6. The production method according to claim 3, wherein 0.45 to 0.55 mol of ethylenediamine is added dropwise to 1 mol of phenylphosphonic acid. 7. A flame-retardant resin composition comprising 100 parts by weight of the resin and 1 to 150 parts by weight of the ethylenediamine-phenylphosphonate according to claim 1 or 2.