JPS6144896A - Preparation of aminomethyl phophonate compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound capable of giving phenolic resins having superior heat resistance and properties, by reacting a polyamine having two primary amino groups with formaldehyde, trialkylphosphite, etc. in a specific ratio, followed by elimination of an alcohol. CONSTITUTION:(A) 1mol polyamine (example; ethylenediamine, etc.) expressed by formula I (R<2> is 2-6C alkylene; n is 1-6) is reacted with (B) 1.8-2.2mol (in terms of formaldehyde) formaldehyde or its derivatives and (C) 1.8-2.2mol trialkyl phosphite (example; triethyl phosphite, etc.) expressed by formula II (R<1> is 1-4C alkyl) preferably in a solvent at 40-120 deg.C, and about 2mol alcohol is eliminated to obtain the aimed aminomethylphosphonate expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a phosphorus compound suitable for improving synthetic resins.

More specifically, the present invention relates to a method for producing an aminomethylphosphonate compound suitable for improving the physical properties of synthetic resins, particularly phenol resins, evo-resin resins, and urethane resins, particularly flame resistance.

[Conventional technology]

The flame-retardant properties of synthetic resins that have been carried out so far include tetrabisphenol A,) licresyl phosphate,)
The method of adding halogen or phosphorus compounds such as liphenyl phosphate and ammonium phosphate has been used, but in order to obtain sufficient flame resistance, the amount added increases, resulting in a decrease in mechanical strength, electrical properties, interlayer adhesion strength, etc. Decrease in punching workability, etc.
Diethyl-N was used as a method to improve these problems.

Method for adding and reacting N-bis(2-hydroxyethyl)aminomethylphosphonate (JP-A-56-49722
However, the reactivity of this compound with phenols and aldehydes is low, and no fundamental solution has been reached.

[Problem that the invention seeks to solve]

The present invention relates to the production of phosphorus compounds that substantially react with phenols and aldehydes, specifically aminomethylphosphonate compounds containing two or more -NH groups; , the above-mentioned problems are solved at once.゛For example, when obtaining a phenolic resin mainly composed of phenols and aldehydes, if the aminomethylphosphonate compound containing two or more -NH groups obtained by the present invention is added and reacted, physical properties and processability can be improved. It is possible to obtain a phenolic resin with excellent flame resistance.

On the other hand, the compounds of the present invention are also useful for making epoxy resins flame resistant. That is, since it is a phosphorus compound containing two or more -NH groups that are highly reactive with epoxy groups, it can be used as a curing agent for a flame release layer.

It is also particularly useful as a reactive flame release agent for urethane resins, and compared to conventional flame release agents, it is more resistant to hydrolysis, has higher reactivity, is polyfunctionalized, and has a higher phosphorus content. is one of its features.

[Means for solving problems]

The requirements for the structure of the present invention are that formaldehyde or its derivatives should be mixed in 1 mole of formaldehyde or a derivative thereof in terms of formaldehyde for 1 mole of a polyamine containing two primary amino groups represented by the following formula (II).
．． 8 to 2.2 moles, t-1,8 to 2.2 moles of the trialkyl phosphite represented by the following formula (II) were reacted, and about 2
The following formula (
An object of the present invention is to produce an aminomethylphosphonate compound represented by II1.

R7 (R1; an alkyl group having 1 to 4 carbon atoms which may be different from each other; R2; an alkylene group having 2 to 6 carbon atoms n; 1 to 6) Phosphorus compounds represented by the general formula (II) have so far been Although it is thought that it is impossible to obtain economically with high purity and good yield, the present inventor has discovered that the polyamine represented by the above formula (υ), formaldehyde or its derivative, and the above formula (II)
By reacting the trialkyl phosphite represented by and removing the by-product alcohol,
They discovered that it is possible to manufacture it.

The reaction formula is shown below.

(II) + 2 HCHO
No. 805, etc., but the purpose is to obtain a phosphorus compound containing a human tetraxyl group, and dialkanolamines (secondary amines) are used as alkanolamines). No specific example of noalkylamine (class II amine) is given.

As an example of the use of monoalkanolamine (class II amine), there is Japanese Patent Publication No. 47-27496, but dialkyl phosphite is used as the phosphite.
As is clear from the comparative examples described below, the phosphorus compound containing two or more monoNH groups and two amine methylphosphonate groups, which is the object of the present invention, cannot be obtained by any of the known methods.

Examples of the polyamine used in the present invention include ethylenediamine, diethylenetriamine, pentaethylenehexamine, propylenediamine, and hexamethylenediamine.

Examples of formaldehyde derivatives include 95% paraformaldehyde and 86% paraformaldehyde.

Examples of the trialkyl phosphite include trimethyl phosphite, triethyl phosphite, diethylisopropyl phosphite, and tributyl phosphite.

The molar ratio of polyamine:formaldehyde:trialkyl phosphite used is substantially 1=2:2), and even if each of them increases or decreases by about 10% relative to other raw materials, there will be no problem in production or use. For example, if the molar ratio is 1:3:3, the gelation reaction will proceed, and if the molar ratio is 1:1:
In No. 1, unreacted amine remains and the desired reaction does not proceed.

The reaction temperature is preferably 40 to 120C in view of color deterioration of the product and efficiency of removing reaction heat.

In order to lower the reaction temperature, it is better to use a solvent, and if the solvent is the same alcohol as the alcohol that is eliminated during the reaction, it will be advantageous in terms of utilization after recovery.

The removed alcohol and solvent are preferably removed and recovered by distillation at 40 to 120 C under normal pressure or reduced pressure.

When the aminomethylphosphonate compound obtained in the present invention is used in a resin, the amount used is preferably 5 to 40% by weight.

〔Example〕

Examples, comparative examples, and usage examples are shown below. Note that parts in the examples are based on weight.

Production of aminomethylphosphonate compound [Example-1] 60 parts of ethylenediamine as the reactant and 50 parts of ethanol as the solvent, 50~(95% while maintaining SOC)
63.2 parts of paraformaldehyde was added and reacted.

The time required was 30 minutes.

Next, 332 parts of triethyl phosphite was introduced over 1 hour at 70 to 80C, and the mixture was further stirred at the same temperature for 2 hours.

The product obtained by removing volatile components under normal pressure and then under reduced pressure was a pale yellow liquid and the yield was 358 parts (yield 99.4%). The fraction was 123 parts, as a result of gas chromatography analysis,
It turned out to be ethanol containing dry water. The analytical values of the product are listed in Table-1. Also, I of this product
The R spectrum is shown in FIG.

These results show that a compound of the following formula was obtained.

[Example-2 to -5] The following compounds were obtained in the same manner as in Example-1.

Manufacturing data and analysis results are summarized in Table 1 @Example-
2 Example-3 Example-4 Example-5 [Comparative Example-1] 60 parts of ethylene diamine, 30 parts of ethanol, 65.2 parts of 95% paraformaldehyde, and 276 parts of diethyl phosphite were mixed with Example-1. The same treatment was performed to obtain 302 parts of a reddish-orange viscous product. The IR chart of the product showed a large absorption near 2400 crn, indicating that the desired reaction did not proceed.

[Usage Example-1] 150 parts of phenol, 156 parts of 57% formalin, 50 parts of the aminomethylphosphonate compound obtained in Example-1, and 6 parts of 26% ammonia were reacted at reflux temperature for 1 hour.

After dehydration under reduced pressure, the mixture was diluted with methanol to obtain a varnish with a resin content of 50%.

A 0.25 m thick kraft paper was impregnated with this varnish to a resin content of 50% and dried.

Laminated the obtained Gribregutsu sheet and one sheet of copper foil to form 16001
00k)/i was pressed for 1 hour to obtain a copper clad laminate with a thickness of 1.61111〇The test results of this product are listed in Table 2◇[Usage Example-2
~5] [Comparative use example 1] A predetermined amount of the methyl phosphonate compound obtained in Examples 2 to 5 and a commercially available additive type flame retardant were added to a phenolic resin varnish with a solid content of 50%, and the mixture was diluted with methanol to a solid content of 50%. %.

Using this varnish, a copper-clad laminate was obtained in the same process as in Use Example-1.

Table 2 shows the amount of the methyl phosphonate compound, the amount of added fuel, and the test results of the obtained laminate.

Production of epoxy resin [Usage Examples - 6, 7, 8] [Comparative Usage Examples - 2, 3] Commercially available bisphenol-based liquid Evo* resin (epoxy equivalent: 1
A predetermined amount of metaxylene diamine, a flame retardant, and a catalyst were added to 90), and the mixture was left to cure at room temperature.

Table 6 shows the blending ratio of each raw material, curing state, etc.

Production of urethane resin [Usage example-9] Aminomethylphosphonate compound 40 obtained in Example-1
parts, 60 parts of polyoxypropylene shoerose with a hydroxyl value of 502 to KOH/l, 21 parts of trichloromonofluoromethane, 3.0 parts of silicone foam stabilizer, 0 parts of amine catalyst
．． 6 parts were mixed and used as the "t-A component." 140 parts of polyphenylene polymethylene polyisocyanate was used as the B component.

Rapidly mix A component and B component, pour into an open mold, react and foam, density 0.03817crt+
It is a urethane foam TI with a uniform temperature of 3.

A combustion test of this product revealed that it was not combustible.

[Comparative Use Example-4] The same process as Use Example-9 was carried out except that 40 parts of diethylbis(hydroxyethyl)aminomethylphosphonate was used instead of the aminomethylphosphonate compound obtained in Example-1.

The results showed that the foaming reaction was slow and the resulting foam had rough cells. In addition, the combustion test resulted in self-extinguishing.

〔Effect of the invention〕

The effect of the present invention is that it provides compounds useful for making phenol resins, epoxy resins, urethane resins, etc. flame resistant.

[Brief explanation of drawings]

FIG. 1 is an IR spectrum of the product obtained in Example-1.

Claims (1)

[Scope of Claims] For 1 mole of a polyamine containing two primary amino groups represented by the following formula (I), 1.8 to 2.2 moles of formaldehyde or a derivative thereof in terms of formaldehyde, ) trialkyl phosphite represented by 1.8
A method for producing an aminomethylphosphonate compound represented by the following formula (III), which comprises reacting with ~2.2 moles and eliminating about 2 moles of alcohol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) R^1; Alkyl with 1 to 4 carbon atoms R^2 which may be different in groups; alkylene group n having 2 to 6 carbon atoms; 1 to 6