KR100609419B1 - Functional organic phosphorous compound and method of preparing same - Google Patents

Abstract

The present invention relates to a functional organophosphorus compound and a preparation method thereof, wherein the functional organophosphorus compound is represented by the following formula (1).

[Formula 1]

(In Formula 1, R ¹ is a 4-allyloxyphenyl group (allyl), 4-metall (methallyl) oxyphenyl group, 3-allyl-4-hydroxyphenyl group or 3-metalloxyoxy hydroxyphenyl group R ² and R ³ are the same or independently of each other, an allyl group, a metalyl group, 4-allyloxyphenyl group, 4-metalloxyphenyl group, 3-allyl-4-hydroxyphenyl group or 3-metall-4 -Represents a hydroxyphenyl group, n represents 0 or 1.)

Epoxy Resin, Functional Organic Phosphorus Compound, Hardener, Flame Retardant, PFM

Description

FUNCTIONAL ORGANIC PHOSPHOROUS COMPOUND AND METHOD OF PREPARING SAME

1 is a graph showing an infrared absorption spectrum of 4-allyloxyphenyldiallylphosphine oxide prepared in Example 1. FIG.

2 is a graph showing ³¹ P { ¹ H} NMR results of 4-allyloxyphenyldiallylphosphine oxide prepared in Example 1. FIG.

Figure 3 is a graph showing the ¹ H NMR results of 4-allyloxyphenyldiallylphosphine oxide prepared in Example 1.

Figure 4 is a graph showing the infrared absorption spectrum of the 4-metal aryl phenyl dimetal yl phosphine oxide prepared in Example 2.

FIG. 5 is a graph showing ³¹ P { ¹ H} NMR results of 4-metalloxyphenyldimetallphosphineoxide prepared in Example 2. FIG.

Figure 6 is a graph showing the ¹ H NMR results of the 4-metal aryl phenyl dimetal yl phosphine oxide prepared in Example 2.

7 is a graph showing infrared absorption spectra of tris- (4-allyloxyphenyl) phosphine prepared in Example 3. FIG.

8 is a graph showing ³¹ P { ¹ H} NMR results of tris- (4-allyloxyphenyl) phosphine prepared in Example 3. FIG.

9 is a graph showing the ¹ H NMR results of tris- (4-allyloxyphenyl) phosphine prepared in Example 3. FIG.

10 is a graph showing an infrared absorption spectrum of tris- (4-allyloxyphenyl) phosphine oxide prepared in Example 4. FIG.

11 is a graph showing ³¹ P { ¹ H} NMR results of tris- (4-allyloxyphenyl) phosphine oxide prepared in Example 4. FIG.

12 is a graph showing the ¹ H NMR results of the tris- (4-allyloxyphenyl) phosphine oxide prepared in Example 4. FIG.

FIG. 13 is a graph showing an infrared absorption spectrum of 3-allyl-4-hydroxyphenyldiallylphosphine oxide prepared in Example 5. FIG.

14 is a graph showing ³¹ P { ¹ H} NMR results of 3-allyl-4-hydroxyphenyldiallylphosphine oxide prepared in Example 5. FIG.

15 is a graph showing the ¹ H NMR results of 3-allyl-4-hydroxyphenyldiallylphosphine oxide prepared in Example 5. FIG.

FIG. 16 is a graph showing an infrared absorption spectrum of 3-metall-4-hydroxyphenyldimetallylphosphine oxide prepared in Example 6. FIG.

FIG. 17 is a graph showing ³¹ P { ¹ H} NMR results of 3-metall-4-hydroxyphenyldimetallphosphineoxide prepared in Example 6. FIG.

FIG. 18 is a graph showing the ¹ H NMR results of 3-methyl-4-hydroxyphenyldimetallylphosphine oxide prepared in Example 6. FIG.

19 is a graph showing infrared absorption spectra of tris- (3-allyl-4-hydroxyphenyl) phosphine oxide prepared in Example 8. FIG.

20 is a graph showing ³¹ P { ¹ H} NMR results of tris- (3-allyl-4-hydroxyphenyl) phosphine oxide prepared in Example 8. FIG.

21 is a graph showing the ¹ H NMR results of tris- (3-allyl-4-hydroxyphenyl) phosphine oxide prepared in Example 8. FIG.

[Industrial use]

The present invention relates to a functional organophosphorus compound and a method for producing the same, and more particularly, to a functional organophosphorus compound and a method for producing the organic polymer compound that can serve as both a crosslinking agent and a flame retardant.

[Prior art]

Organophosphorus compounds are usefully used as stabilizers, plasticizers, or flame retardants of organic polymer compounds, and are also widely used as special surfactants, extreme pressure additives, or pesticides. Among these various uses, it is especially drawing attention as a flame retardant of a high molecular compound. The reason is that organic halogen compounds, which are conventionally used as flame retardants of polymer compounds, generate toxic gases when fire occurs and burn, and when incinerated, corrode incinerators and release environmentally harmful harmful substances. Because there is a problem. Therefore, in the industry using a flame retardant, a research for using an organophosphorus compound as a flame retardant is being progressed in the active movement to replace this organic halogen compound flame retardant with another flame retardant.

Phosphoric acid ester-based organophosphorus compounds are mainly used as organophosphorus compounds developed as flame retardants. However, the phosphate ester-based organophosphorus compound is prone to hydrolysis in the presence of high temperature moisture or alkali in the polymer material, and the hydrolysis product degrades the electrical insulation of the polymer material and, in extreme cases, is finely installed on the substrate of the polymer material. There is a problem of corroding electrical wiring.

Therefore, in order to use an organic phosphorus compound in the electrical component or an electromagnetic component which requires electrical insulation, development of the organic phosphorus compound which has non-hydrolysis property is urgently required.

In addition, research on the organophosphorus compound which also functions as a crosslinking agent of a thermoplastic resin is progressing. The thermosetting resins, such as phenolic resin, melamine resin, unsaturated polyester or epoxy resin, have been used in the manufacture of device parts, electrical parts, or electronic devices requiring high heat resistance, but these thermosetting resins have a long curing time. There is a disadvantage in that productivity is poor, there is a limit to miniaturization or precision of parts, and there is a disadvantage of lighting that product uniformity is not sufficient, and research for replacing a thermosetting resin has recently been conducted. The thermosetting resin is formed by forming a crosslinked structure in the thermoplastic resin by performing radiation treatment such as electron beam and gamma ray on the manufactured molded article. Since the thermoplastic resin has lower heat resistance than the thermosetting resin, the thermoplastic resin is added with a flame retardant to improve heat resistance. It is made to provide the heat resistance of the thermosetting resin grade. In recent years, studies have been made to have a crosslinking agent also have a function as a flame retardant. Therefore, studies have been made to use the organic phosphorus compound usable as a flame retardant as a crosslinking agent and to use it as a crosslinking agent and a flame retardant of a thermoplastic resin. As described above, the organophosphorus compound acting as a flame retardant has a plurality of unsaturated groups in order to act as a crosslinking agent, and is crosslinked with the polymerization or organic polymer compound by radiation treatment such as a polymerization initiator, infrared ray, electron beam or gamma ray. Development of organophosphorus compounds capable of forming bonds is being studied.

In addition, self-crosslinkable thermoplastic resins such as polyethylene or some rubbers can be crosslinked by radiation treatment without using a crosslinking agent to obtain thermoplastic, but self-crosslinkable such as polypropylene, polystyrene, polycarbonate resin, polyphenylene oxide resin or polyamide resin, etc. In many thermoplastic resins that do not have a thermoplastic resin, a component is prepared by adding an organic compound called a polyfunctional monomer (PFM) as a crosslinking agent prior to the radiation treatment, and then subjected to radiation treatment such as an electron beam or a gamma ray to improve the appearance of the components. It should give the desired heat resistance without making a complete change.

The PFM (hereinafter, referred to herein as a crosslinking agent for the purpose of radiation treatment simply referred to as PFM) is an organic compound having a polyunsaturated group and must be compatible with the target thermoplastic resin. Therefore, if there are a plurality of unsaturated groups in the organophosphorus compound, it is expected to include a function as a flame retardant and a function as PFM. As such organophosphorus compounds, triallyl phosphate (triallyl phosphate) is well known at present, but it has a low molecular weight, is volatile, and is easily used as it is easily hydrolyzed. Therefore, the development of flame-retardant PFM made of a non-hydrolyzable organophosphorus compound suitable for this technique is expected.

In addition, the non-hydrolyzable organophosphorus compound having a plurality of phenolic hydroxyl groups is a hardening agent for epoxy resins, which is important for use in electrical parts or electronic device parts such as those disclosed in Japanese Patent Application Laid-Open No. 2000-186186, and the like. This is expected.

It is an object of the present invention to provide a functional organophosphorus compound having a non-hydrolyzable property which can be used as a flame retardant in electrical parts or electronic device parts.

Another object of the present invention is to provide a functional organophosphorus compound usable with flame retardant PFM.                         

Still another object of the present invention is to provide a functional organophosphorus compound which can be used for various purposes by utilizing the reactivity of an unsaturated group or a hydroxyl group of the functional organophosphorus compound.

Another object of the present invention is to provide a method for producing a functional organophosphorus compound having the above-described physical properties.

In order to achieve the above object, the present invention provides a functional organophosphorus compound represented by the following formula (1), comprising three unsaturated groups in the molecule.

[Formula 1]

(In Formula 1, R ¹ represents a 4-allyloxyphenyl group, 4-methylloxyphenyl group, 3-allyl-4-hydroxyphenyl group, or 3-metallyloxy-4-hydroxyphenyl group, R ² and R ³ are the same or independently of each other, an allyl group, metalyl group, 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group or 3-metall-4-hydroxy A phenyl group, n represents 0 or 1.)

The present invention also provides a process for preparing the functional organophosphorus compound of Chemical Formula 1 including the step of condensation reaction of the organophosphorus compound of Chemical Formula 2 with a Grignard reagent.

[Formula 2]

In the above formula (2), R ⁴ represents a 4-allyloxyphenyl group or 4-metallyloxyphenyl group, X is a chlorine atom, bromine atom or phenoxy group and m represents 0 or 1.

The invention also provides 4-allyloxyphenyldiallylphosphineoxide or 4-metallyloxyphenyldimetallylphosphine oxide, tris- (4-allyloxyphenyl) phosphine and tris- (4-allyloxyphenyl) force. It provides a method for producing a flame-retardant, heat-resistant polycarbonate molded article comprising the step of irradiating a polystyrene-polyphenyl dioxide resin molded article containing 1 to 25% by weight of a functional organophosphorous compound selected from the group consisting of pin oxide.

The invention also provides 3-allyl-4-hydroxyphenyldiallylphosphineoxide, 3-metall-4-hydroxyphenyldimetallylphosphine oxide, tris- (3-allyl-4-hydroxyphenyl) force Flame retardancy comprising the step of irradiating a polyamide molded article comprising 2 to 25% by weight of a functional organophosphorous compound selected from the group consisting of fin and tris- (3-allyl-4-hydroxyphenyl) phosphine oxide And a method for producing a heat resistant polyamide molded article.

The present invention also provides a flame-retardant epoxy resin composition containing 10 to 40% by weight of the functional organophosphorus compound of Formula 1.

Hereinafter, the present invention will be described in detail.

The present invention relates to a functional organophosphorus compound represented by the following Chemical Formula 1, which can serve as both a flame retardant and a crosslinking agent in the polymer resin composition.

[Formula 1]

In the formula (1), R ¹ represents a 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group or 3-metalloxyoxy-hydroxyphenyl group,

R ² and R ³ are the same or independently of each other, an allyl group, metalyl group, 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group or 3-metall-4-hydroxy A phenyl group is represented and n represents 0 or 1.

Preferred compounds of formula (1) are those in which R ¹ is a 4-allyloxyphenyl group, R ² and R ³ are allyl groups, n is 1 4-allyloxyphenyldiallylphosphine oxide, and R ¹ is 4-metalyloxy Phenyl group, R ² and R ³ are metalyl groups, n is 1, 4-metalyloxyphenyldimetallylphosphine oxide, R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, n is 0 Phosphorus tris- (4-allyloxyphenyl) phosphine, R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, and n is 1, tris- (4-allyloxyphenyl) phosphine oxide.

As shown in Formula 1, the functional organophosphorus compound of the present invention is non-hydrolyzable because all of the phosphorus atoms and three carbon atoms are directly bonded. In addition, since the functional organophosphorus compound has three unsaturated groups and is polymerized by a polymerization initiator, radiation treatment or the like, the functional organophosphorus compound has a function such as a crosslinking reaction with respect to the organic polymer compound, and can be used as a flame retardant PFM.

Moreover, this unsaturated group is rich in reactivity, and an epoxy compound is induced in the oxidation reaction by an oxidizing agent, and a halogen compound is induced in the halogen reaction. In addition, the hydroxyl group of a part of the organophosphorus compound represented by the formula (1) is also rich in reactivity, so that the etherification reaction easily occurs in the presence of an organic halogen compound and an alkali. Of the etherification reactions, the glycidyl etherification reaction is important. Functional organophosphorus compounds having a hydroxy group, in particular tris- (3-allyl-4-hydroxyphenyl) phosphine oxide, have three hydroxyl groups, have a function as a flame retardant curing agent of the epoxy resin, and epihalohi under alkaline residuals Condensation reaction with Drine to form glycidyl ether gives tris- (3-allyl-4-glycidyloxyphenyl) phosphine oxide. Since the product to be produced has non-hydrolyzable properties, it is useful as a flame-retardant epoxy resin composition for use in electric parts or electronic parts. In addition, the ortho position of the hydroxy group is also reactive, and the flame retardant phenol resin is induced by reacting with formaldehyde and the like. As such, the compounds of Formula 1 and derivatives thereof may be applied to various fields.

The functional organophosphorus compound of the present invention is largely divided into a compound having no hydroxy group and a compound having a hydroxy group in the molecule, and their preparation methods, physical properties and uses thereof are different, but any structure may be useful as a polymer flame retardant crosslinking agent. Hereinafter, a method of preparing the functional organophosphorus compound of Chemical Formula 1 of the present invention will be described in detail by distinguishing the compound having a hydroxy group from the compound and the compound having a hydroxy group.

Among the functional organophosphorus compounds represented by the general formula (1), compounds having no hydroxy group in the molecule are prepared by condensation reaction of the organic phosphorus compound of the following general formula (2) with a Grignard reagent.

[Formula 2]

In the formula (2), R ⁴ represents a 4-allyloxyphenyl group or 4-metalloxyoxy group, X is a chlorine element, a boron atom or a phenoxy group, and m represents 0 or 1.

The Grignard reagent is an organometallic compound represented by RMgX (R is a C ₂ to C ₈ alkyl group, a C ₆ to C ₁₄ allyl group, X is a halogen), and representative examples thereof are allyl magnesium halogenide and metalyl magnesium. Halogenide, 4-allyloxyphenylmagnesium halogenide or 4-metallyloxyphenylmagnesium halogenide can be used, but is not limited thereto.

Compounds having no hydroxy group in the molecule according to this process include 4-allyloxyphenyldiallylphosphine, 4-metallyloxyphenyldimetallylphosphine, tris- (4-allyloxyphenyl) phosphine, tris- (4 Phosphine-based compounds such as -metalloxyoxy) phosphine, tris- (4-metalloxyoxy) phosphine or oxides thereof are prepared.

In addition, the phosphine-based compound thus prepared is 4-allyloxy phenyl diallyl phosphine oxide, 4-metall oxy phenyl dimetallyl phosphine oxide, tris- (4-allyloxy phenyl) when the oxidizing reaction is performed with an oxidizing agent. Phosphine, tris- (4-metallyloxyphenyl) phosphine, 4-allyloxyphenyldiallylphosphine oxide, 4-metallyloxyphenyldimetallyl phosphine oxide, tris- (4-allyloxyphenylphosphine Phosphine oxide-based compounds such as oxides or tris- (4-allyloxyphenyl) phosphine oxides, etc. are prepared, as the oxidizing agent may be air, oxygen, hydrogen peroxide, organic peroxides, etc. Among these, air is the most economical Since tris- (4-allyloxyphenyl) phosphine or tris- (4-metallyloxyphenyl) phosphine is not easily oxidized by air, it is preferable to use hydrogen peroxide or organic peroxide. C. As the organic peroxide, acetic acid peroxide or fluoroperoxy acetic acid may be used, etc. The organic peroxide such as acetic acid peroxide may be used directly, but peroxide may be reacted with acetic acid and hydrogen peroxide by using acetic acid and hydrogen peroxide together. Acetic acid can also be formed.

Of course, the phosphine-based or phosphine oxide-based compound is not limited thereto, and all compounds included in the definition of Chemical Formula 1 and having no hydroxy group in the molecule may be included.

It is preferable to perform the condensation reaction in anhydrous inert organic solvent because the reaction proceeds smoothly. Such anhydrous inert organic solvents include ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, pyrane, n-hexane, heptane, nonane, decane, cyclohexane, benzene, toluene, Xylene, trimethylbenzene, ethylbenzene, etc. can be used.

In addition, purification may be carried out such as general washing with water to remove impurities such as magnesium halogenide or magnesium phenoxide, which may be generated after the condensation reaction, and vacuum distillation, recrystallization, etc. This can improve the purity of the phosphine compound or phosphine oxide compound of the desired product. The washing process is carried out with water or diluted acid. According to this process, impurities such as magnesium phenoxide are decomposed into magnesium salts and phenols and removed with inorganic salts, and only organic phosphorus compounds as target products can be obtained.

The ratio of the organophosphorus compound of Formula 2 and the Grignard reagent is preferably 0.5 to 1: 1 to 5 in molar ratio. When the molar ratio of the organophosphorus compound of Formula 2 and the Grignard reagent is outside the above range, the reaction rate decreases and the type and amount of impurities increase, which is not preferable.

As an example of the reaction, when R ⁴ is 4-allyloxyphenyl group, X is phenoxy group, chlorine atom or bromine atom, and m is 0, condensation reaction of 4-allyloxyphenylmagnesium halogenogenide In the general formula (1), R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, and n is 0. Tris- (4-allyloxyphenyl) phosphine is prepared.

As another example of the reaction, the condensation reaction of the organophosphorus compound of Chemical Formula 2 with allylmagnesium halogenide, metalylmagnesium halidenide or 4-allyloxyphenylmagnesium halideide, R ¹ in Formula ¹ This 4-allyloxyphenyl group, R <^2> and R <^3> is an allyl group, n is 1- 4-allyloxy phenyl diallyl phosphine oxide, R <^1> is 4-metall oxy phenyl group, R <^2> and R <^3> together metal Trimethyl- (4-allyloxyphenyl) in which n is 1, 4-methyloxyphenyldimetalyl phosphine oxide in which n is 1, or R ¹ , R ² and R ³ together are a 4-allyloxyphenyl group and n is 1 Phosphine oxide is prepared. At this time, when m is 0, it is good to perform an oxidation reaction further or to carry out a transition reaction in a molecule | numerator.

In addition, among the compounds of Formula 1, n is 1, and the compound having no hydroxy group is phosphoryl trihalide (PX ₃ : X is halogen), phosphite compound, or 1 mole of phosphorus oxychloride (POCl ₃ ). It can also be obtained by condensation reaction with 3 mol of Grignard reagent, ie, the Grignard reaction. At this time, when using a phosphorus trihalide or a phosphite compound, it is good to perform an oxidation reaction further.

The functional organophosphorus compound having no hydroxyl group in the molecule among the functional organophosphorus compounds represented by Formula 1 is prepared by an intramolecular transition reaction of a compound having a hydroxyl group in the molecule prepared according to the above process. This intramolecular transfer reaction is called Claisen rearrangement. The transition reaction may be carried out only by heating the compound having the hydroxy group, but the reaction may be performed by adding an acidic catalyst such as Lewis acid or magnesium or sulfonic acid such as magnesium chloride, aluminum chloride, zinc chloride or ferric chloride. It can also be promoted.

Since the transition reaction is exothermic, it is preferable to carry out the reaction in an inert solvent for the purpose of making the reaction gentle and smooth. Inert solvents include hydrocarbons such as heptane, octane, nonane, decane, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, naphthalin or biphenyl, dichloroethane, trichloroethane, chlorobenzene or cyclo Chlorinated hydrocarbons such as robenzene or nitrobenzene, phenol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, diethylene glycol, diethylene glycol Monomethyl ether, diethylene glycol dimethyl ether, sulfolane, γ-butyrolactone, 1-methyl-2-pyrrolidone or N, N-dimethylimidazolidinone and the like.

When the intramolecular transition reaction is carried out without using a catalyst, relatively high boiling point such as diethylene glycol, sulfolane, γ-butyrolactone, 1-methyl-2-pyrrolidone or N, N-dimethylimidazolidinone, etc. Preference is given to using inert solvents.

The functional organophosphorus compound which does not have a hydroxy group obtained by the intramolecular transition reaction can be purified by a washing process, a recrystallization method or a vacuum distillation method in the same manner as the production process of the compound having a hydroxy group. Examples of the compound having a hydroxy group in the molecule prepared according to this process include 3-allyl-4-hydroxyphenyldiallylphosphine oxide, 3-metall-4-hydroxydimetallylphosphine oxide, tris- (3 -Allyl-4-hydroxyphenyl) phosphine, tris- (3-allyl-4-hydroxyphenyl) phosphine oxide, or tris- (3-metallyl-4-hydroxyphenyl) phosphine oxide, etc. are mentioned. However, the present invention is not limited thereto and may be included in the definition of Chemical Formula 1, and may include any compound having a hydroxyl group in the molecule.

Hereinafter, the process for preparing the compound of Formula 2 used in the process for preparing a compound having no hydroxy group in the molecule will be described in more detail. The organophosphorus compound represented by Chemical Formula 2 may be a condensation reaction, that is, a Grignard reaction (Grignard reagent) with phosphorus trihalide (PX ₃ : X is halogen), a phosphite compound or phosphorus oxychloride (POCl ₃ ). Prepared by Grignard reaction).

The phosphorus trihalide, phosphite compound, or phosphorus oxychloride is preferably used because the condensation reaction occurs smoothly using a solution dissolved in an anhydrous inert organic solvent. The anhydrous inert organic solvent may be ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, pyrane, n-hexane, heptane, nonane, decane, cyclohexane, benzene, toluene , Xylene, trimethylbenzene or ethylbenzene can be used.

Phosphorus trichloride (PCl ₃ ) or phosphorus tribromide (PBr ₃ ) may be used as the phosphorus trihalide, but it is economically preferable to use phosphorus trichloride.

As the phosphite-based compound, such as triphenyl phosphite (triphenyl phosphite), tricresyl phosphite, or monocresyl diphenyl phosphite, dicresyl monophenyl phosphite, cresyl and phenyl are simultaneously included in one molecule. Mixed phosphite and the like can be used, triphenylphosphite or phosphorus oxychloride is preferable since the Grignard reaction can be easily performed and the selectivity in the reaction can be improved.

Since the condensation reaction of the phosphorus trihalide or phosphite compound with the Grignard reagent occurs very vigorously, it is preferable to carry out the condensation reaction in an inert organic solvent and at the lowest possible temperature.

The ratio of the use of the phosphorus trihalide or phosphite compound and the Grignard reagent is preferably 1 mole, i.e., an equimolar amount, of the phosphoride trihalide, phosphite compound or phosphorus oxychloride.

Examples of the Grignard reagent include substituted magnesium halogenogens such as allyl magnesium halogenide, metalyl magnesium halogenide, 4-allyloxyphenyl magnesium halogenide, or 4-metallyloxyphenyl magnesium halogenide. Drew may be used, and such Grignard reagents are prepared by the reaction of organic halogen compounds with metal magnesium. In general, the Grignard reagent preparation process is carried out in the presence of anhydrous ethylene ether or tetrahydrofuran, and among them, tetrahydrofuran is widely used because of its excellent reactivity and advantages in terms of selectivity, yield and reaction time.

That is, the Grignard reagent reacts allylhalogenide, metallylhalogenide, 4-allyloxyphenylhalogenide or 4-metallylphenylhalogenide with metal magnesium in the presence of tetrahydrofuran. Are prepared. The presence of trace amounts of iodine in this reaction is preferred because the reaction occurs smoothly.

The allylhalogenide and metallylhalogenide are preferred because chlorides such as allyl chloride and metallyl chloride are available on an industrial scale, and the greenide reagent can be easily prepared.

In addition, 4-allyloxyphenylhalogenide or 4-metallyloxyphenylhalogenide is only required to be carried out at a higher temperature than tetrahydrofuran under pressure since the reaction with metal magnesium is very gentle. Of these halogenides, bromide compounds such as 4-allyloxyphenyl bromide or 4-metallyloxyphenyl bromide are more reactive than chloride compounds, but in terms of price, chloride compounds are somewhat cheaper than bromide compounds.

4-allyloxyphenylhalogenide or 4-metallyloxyphenylhalogenide is 4-hydroxyphenylchloride (parachlorophenyl) or 4-hydroxyphenylchloride (parabromophenol) and allyl chloride or metal Reyl chloride is prepared by conducting a condensation reaction in the presence of alkali. As the alkali, sodium hydroxide or potassium hydroxide may be used, among which sodium hydroxide is economically preferable. In addition, parachlorophenol may be prepared by chlorination of phenol with chlorine or sulfuryl chloride, but in chlorination with chlorine, many orthochlorophenols are additionally produced and thus the yield tends to be low. Chlorination is carried out with sulfyl chloride. Parabromophenol is produced by brominating phenol, and it is preferable to carry out this bromination at a low temperature because fewer addition products such as orthobromophenol are used.

EMBODIMENT OF THE INVENTION Hereinafter, the industrial utility of this invention is demonstrated.

The functional organophosphorus compound of the present invention can be used in a variety of industries, and in the functional organophosphorus compound of the formula (1) does not have a hydroxy group in the molecule and having a hydroxy group, that is can be used separately depending on the structure, but any structure Even if it has a flame retardant PFM, that is, it can be usefully used as a flame retardant crosslinking agent.

4-allyloxyphenyldiallylphosphine oxide, 4-methyloxyphenyldimetallylphosphine oxide, tris- (4-allyloxyphenyl) phosphine, which are functional organophosphorus compounds of the present invention having no hydroxy group in the molecule, and Tris- (4-allyloxyphenyl) phosphine oxide, preferably 4-allyloxyphenyldiallylphosphine oxide or 4-metallyloxyphenyldimetallylphosphine oxide is a polycarbonate resin, a polycarbonate resin and a polystyrene. It is compatible with various thermoplastic resins such as mixed polyphenyl dioxide resin, polyphenylene sulfide, polyethylene, polypropylene, polystyrene, AS resin, ABS resin or polyvinyl chloride resin, and can be used as these PFM. In particular, the flame retardant effect by the functional organophosphorus compound of the present invention is maximized when used as the PFM of the polyphenylene dioxide resin mixed with polycarbonate resin and polystyrene.

That is, when the functional organophosphorus compound of this invention is added to the said resin, and it shape | molds and radiation treatment is carried out, a crosslinked structure will be formed in resin and it can give higher heat resistance. As the radiation, an electron beam or a gamma ray can be used, and among these, gamma ray by cobalt 60 has a large transmission power and is easy to use.

The compound of the present invention enables the formation of a crosslinked structure and impart flame retardancy at the same time, and the content of the functional organophosphorus compound having no hydroxy group of the present invention is 1 to 25% by weight, more preferably 2 to 2, based on the resins. 15% by weight.

In addition to the functional organophosphorus compound of the present invention, a suitable additive is added to the flame-retardant epoxy resin composition, respectively. Examples of the additive include colorants such as stabilizers, swelling agents, other flame retardants, dyes, paints, and inorganic fillers.

3-allyl-4-hydroxyphenyldiallylphosphine oxide which is a functional organophosphorus compound having a hydroxy group in a molecule, 3-metall-4-hydroxyphenyldimetallylphosphine oxide, tris- (3-allyl-4 -Hydroxyphenyl) phosphine or tris- (3-allyl-4-hydroxyphenyl) phosphine oxide, preferably 3-allyl-4-hydroxyphenadiallylphosphine oxide, 3-metall-4- Hydroxyphenydimetall phosphine oxide or tris (3-allyl-4-hydroxyphenyl) phosphine oxide is particularly excellent in compatibility with polyamide resin, and is effective as a flame retardant PFM for polyamide resin. However, since tris- (4-allyloxyphenyl) phosphine oxide relatively easily undergoes intramolecular transition reactions, when appropriate temperature and time are given during the mixing or molding operation, tris- (3-allyl is used when used for polyamide resins. The same effect as that of 4-hydroxyphenyl) phosphine oxide can be obtained.

Examples of the polyamide resins include 6-nylon, 6,6-nylon, 6,10-nylon, 6,12-nylon, 11-nylon, 12-nylon or copolymerized nylon. These polyamide resins have physical properties that are excellent in toughness, abrasion resistance, self-swelling, vibration absorption or oil resistance, and start with textile fabrics, such as automobile parts, machine parts, building materials, electrical parts, electronics, etc. It is widely used in equipment parts, medical supplies, household goods, and the like. However, in applications such as electric parts or electronic device parts, high heat resistance such as melt soldering is required, that is, high heat resistance is required, but polyamide resins do not have sufficient heat resistance.

Therefore, in the case where a polyamide resin is used for applications requiring heat resistance, a technique of radiation treatment is performed on components formed by mixing and molding PFM, and a technique having heat resistance equivalent to that of a thermosetting resin is currently being implemented. As such PFM, 1,3,5-triacryloylhexahydro-S-triazine (triacrylform) is known, but this compound does not have a flame retardant function, and thus an organic halogen compound such as brominated polystyrene is further added as a flame retardant. Should. However, the functional organophosphorus compound having a hydroxy group of the present invention is excellent in compatibility with the polyamide resin, and also plays a role as a flame retardant and a crosslinking agent, so there is no need to use a separate flame retardant. The content of the functional organophosphorus compound in the flame retardant polyamide resin composition comprising the functional organophosphorus compound having a hydroxy group of the present invention is 2 to 25% by weight, more preferably 4 to 15% by weight. When the resin composition is molded and subjected to radiation treatment such as γ-rays, the resin composition can have heat resistance and flame retardance to melt soldering at the same time.

Specifically, the melting point of 6,6-nylon is about 260 ° C., and it is not self-extinguishing, but 3-allyl-4-hydroxyphenyldiallylphosphine oxide and 3-metall-4-hydroxy are added thereto. 4-15% by weight of phenyldimetallphosphineoxide, tris- (3-allyl-4-hydroxyphenylphosphine) or tris- (3-allyl-4-hydroxyphenyl) phosphine oxide is added to UL- After the 94 test piece was molded, the molded product was irradiated with γ-ray, and the heat resistance was 300 ° C. or higher, and it was confirmed that a flame retardant polyamide resin corresponding to V-1 of UL-94 was obtained in the flame resistance test.

The flame retardant polyamide resin composition may contain various additives in addition to the functional organophosphorus compound of the present invention. Examples of the additive include stabilizers, other flame retardants, other PFMs, swelling agents, paints, colorants such as dyes, and inorganic fillers. In particular, when the inorganic flame retardant and the inorganic filler are added in an amount of 10% by weight or more relative to the polyamide resin, heat resistance and flame retardancy can be further improved. The inorganic flame retardant and the inorganic filler may be used up to 80% by weight. As the inorganic flame retardant, magnesium hydroxide, aluminum hydroxide, red phosphorus, hydrotalcite, or the like may be used, and as the inorganic filler, glass fiber, carbon black, hydrotalcite, magnesium hydroxide, or the like may be used.

In addition, the functional organophosphorus compound of the present invention is made of an epoxy resin or a phenol resin, and is mainly required for flame retardancy and can be usefully used for printed wiring boards used in electronic components.

In the functional organophosphorus compound of the general formula (1) of the present invention, the compound having no hydroxyl group in the molecule has three unsaturated groups and epoxidizes with an oxidizing agent to produce a triepoxy compound having a non-hydrolyzable epoxy resin used for a printed wiring board. It can be used in the composition. As the oxidizing agent, hydrogen peroxide, peracid or hypersulfite chloride may be used.

In addition, among the functional organophosphorus compounds represented by the general formula (1), the compound having a hydroxy group in the molecule is excellent in solubility in organic solvents such as methyl ethyl ketone, dimethylformamide or N, N-dimethylacetoamide, and thus as a flame retardant curing agent for epoxy resins. Can be used. In the flame retardant epoxy resin composition comprising the compound of the present invention, the content of the compound of the present invention is preferably 10 to 40% by weight, more preferably 20 to 35% by weight relative to the cured epoxy resin. The obtained composition obtained flame retardancy corresponding to V-0 in the flame retardancy test method of UL-94.

BACKGROUND ART In recent years, the miniaturization of wirings and their multilayering have progressed in printed wiring boards. Since the functional organophosphorus compound of the present invention is non-hydrolyzable, the electrical properties of the substrate using the same are not deteriorated even under severe conditions.

In addition, the functional organophosphorus compound having three hydroxyl groups in the molecule may be condensed with epichlorohydrin in the presence of alkali to prepare a trivalent epoxy compound, and such an epoxy compound may also be usefully used for an epoxy resin for a printed wiring board. .

The functional organophosphorus compound having three hydroxyl groups in the molecule of the present invention forms an excess of formaldehyde and a resol-type phenol resin intermediate as a trivalent phenol, and then uses this intermediate to produce a phenol resin. Therefore, when the phenol resin is prepared using 5 to 30% by weight of the compound of the present invention, more preferably 10 to 25% by weight, and cured, the flame retardancy corresponding to V-0 is obtained in the test method of UL-94. Can be. This flame-retardant phenol resin is suitable also for the use of various electrical components or electronic components for a printed wiring board, and electrical insulation does not fall by hydrolysis.

The functional organophosphorus compound which does not have a hydroxyl group in a molecule | numerator has a function as a reactive flame retardant of unsaturated polyester resin. In the flame retardant unsaturated polyester resin composition comprising the compound of the present invention, the content of the compound of the present invention is preferably 3 to 20% by weight relative to the unsaturated polyester resin. Unsaturated polyester resins include unsaturated dibasic acids and succinic acid, adipic acid, sebacic acid, phthalic acid or the like which are less self-polymerizable in strong polarities such as maleic acid, fumaric acid, itaconic acid or citraconic acid. Essentially obtained by ester reaction with dibasic acids which do not have an unsaturated group such as isophthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol or neopentyl glycol It is a kind of thermosetting material which is a mixture of a linear polymer and vinyl monomers such as styrene, vinyl toluene, diallyl phthalate, triallyl trimellitic acid, triallyl phosphate or triallyl phosphate, and a curing initiator in the presence of a polymerization initiator or polymerization accelerator. Resin. They are used for paints, castings, or fiber-reinforced materials, and are widely used in solvent-free paints, electric parts, automobile parts, decorative plates, substrates, bathtubs, modulators, septic tanks, and ships. Conventionally, halogen-containing dibasic acids and the like are used as the flame retardant, but the functional organophosphorus compound of the present invention has a plurality of allyl groups, and in the unsaturated polyester resin, it is used in the same manner as the vinyl monomer to impart flame retardancy. .

Of the functional organophosphorus compounds represented by the formula (1), n is 0 phosphines, especially tris- (4-allyloxyphenyl) -phosphine and tris- (3-allyl-4-hydroxyphenyl) phosphine It is added as a stabilizer of propylene or synthetic rubbers to form a stabilized polypropylene composition or synthetic rubber composition.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples. In the following examples, comparative examples and reference examples, "%" represents weight% and "part" represents parts by weight.

Example 1 Synthesis of 4-allyloxyphenyldiallylphosphine oxide

Example 1-1 (Synthesis of 4-allyloxyphenylbromide)

Into a 5,000 ml glass four-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping rod, 1,211 g (7 mol) of 4-bromophenol and 1,000 g (7.5 mol) of 30% aqueous sodium hydroxide solution were stirred and stirred. While maintaining the temperature of the contents at 80 ° C, 551 g (7.2 mol) of allyl chloride was slowly added dropwise through a dropping rod. The dropping was adjusted for about 6 hours by adjusting the dropping at a rate of slightly refluxing allyl chloride from the reflux condenser. After completion of the dropping, the contents were sampled every hour to confirm the progress of the reaction by gas chromatography (GC) analysis. In addition, since the raw material 4-bromophenol was completely lost after 4 hours, 1,200 g of water and 800 g of toluene were added to the product, the mixture was stirred again, and left to stand to remove the lower water layer. 1,000 g of 1% sodium hydroxide aqueous solution was continuously added, it stirred for 30 minutes, and it left still to obtain only an oil layer. Toluene was distilled off from the oil layer and vacuum distilled under reduced pressure of about 0.6 kilopascal to obtain about 1,400 g of 4-allyloxyphenylbromide.

Example 1-2 Synthesis of 4-allyloxyphenylmagnesium halogenide

A vacuum in the flask was replaced by blowing nitrogen gas through a gas inlet into a 3,000 ml glass four-necked flask equipped with a stirrer, thermometer, reflux cooler, gas inlet and dropping rod. 500 g of tetrahydrofuran, 87.6 g (3.6 mol) of metal magnesium, and 0.1 g of iodine were injected therein, followed by stirring to slowly blow nitrogen gas. 200 g of 4-allyloxyphenylbromide 32% tetrahydrofuran solution was added from the dropping rod. After stirring for 2 hours at room temperature, the flask was heated to maintain the temperature at which the contents boiled, and 1,800 g of 4-allyloxyphenylbromide 32% tetrahydrofuran solution was added dropwise for 2 hours through a dropping rod. The boiling condition was maintained for 1 hour and excess metal magnesium was filtered off. At this time, the temperature was 65-70 degreeC. This was cooled to prepare a tetrahydrofuran solution of 4-allyloxyphenylmagnesium bromide.

Example 1-3 Synthesis of 4-allyloxyphenyldiphenoxyphosphine

Nitrogen gas was sucked through a gas inlet into a 6,000 ml hard glass five-necked flask with a stirrer, thermometer, reflux cooler, gas inlet, dropping rod, and liquid outlet at the bottom to replace air in the flask. 1,000 g of toluene and 465 g (1.5 mol) of triphenyl phosphite were injected therein, nitrogen gas was gradually blown from the gas inlet, and stirred to maintain the temperature of the flask contents at 20 to 30 ° C. Here, half the amount of the tetrahydrofuran solution of 4-allyloxyphenylmagnesium halidenide obtained in Example 1-2 was added dropwise through a dropping rod for 1 hour. Subsequently, the product was recessed at this temperature for 1 hour to confirm the production of 4-allyloxyphenyldiphenoxyphosphine by GC analysis.

Example 1-4 (Synthesis of 4-allyloxyphenyldiallylphosphine)

The flask contents of Example 1-3 were stored at 20-30 degreeC, and 3 mol of the tetrahydrofuran solutions of the allyl magnesium chloride (Aldrich reagent) were dripped over 3 hours through the dripping load. It was recessed for 1 hour to confirm 4-allyloxyphenyldiallylphosphine production by LC analysis. 1,200 g of 10% aqueous sulfuric acid solution was added dropwise thereto for 30 minutes. Then, the mixture was stirred for 30 minutes and allowed to stand for 30 minutes. The lower water layer was removed, 1,600 g of purified water was added thereto, stirred for 30 minutes, and allowed to stand for 30 minutes. After removing the water layer again, tetrahydrofuran, toluene and phenol were distilled off under reduced pressure to prepare about 360 g of purified 4-allyloxyphenyldiallylphosphine. The obtained product was confirmed to be the target compound by ³¹ P NMR and ¹ H NMR.

Example 1-5 (Synthesis of 4-allyloxyphenyldiallylphosphine oxide)

350 g of 4-allyloxyphenyldiallylphosphine obtained in Example 1-4 was injected into a 500 ml rigid four-necked flask equipped with a stirrer, a thermometer, a gas inlet, and a reflux remover, and the flask was heated while stirring. The temperature of was 100 degreeC. A small amount of the same amount mixed gas of dry air and nitrogen gas was blown in from the gas inlet. After about 10 hours, GC analysis confirmed that 4-allyloxyphenyldiallylphosphine was completely changed to 4-allyloxyphenyldiallylphosphine oxide. It was transferred to a 500 ml packed distillate with a volume of 5 centimeters in diameter and 25 centimeters in height packed with a heated Raschigring (used as a filler for the separation of the distillation column) and distilled under a pressure of about 200 Pascals, About 330 g of alcohol content 4-allyloxyphenyl diallyl phosphine oxide was obtained. The infrared absorption spectrum is shown in Fig. 1, ³¹ P { ¹ H}. NMR is shown in Figure 2 and ¹ H NMR is shown in FIG. 3. The elemental analysis showed that the product was 4-allyloxyphenyldiallylphosphine oxide because the carbon was 68.8% (theoretical: 68.69%), hydrogen was 7.3% (theoretical: 7.302%), and phosphorus was 11.9% (theoretical: 11.81%). It was confirmed that it was. However, the infrared absorption spectrum prepared the sample using KBr, and the absorption peak considered to be -OH group was confirmed slightly on the spectrum. However, since no -OH peak was found on ¹ H NMR, it was confirmed that a small amount of -OH peak appearing in the infrared absorption spectrum was due to moisture absorption during KBr operation. Meanwhile, ¹ H NMR used a CDCl ₃ solvent, a chemical shift (TEM) was used as a reference material for chemical shift determination, and ³¹ P { ¹ H} proton decoupled (PMR) used phosphoric acid as a reference for chemical shift. Used as a material. In the following examples, these methods were used as long as there were no special problems.

Example 2 (Synthesis of 4-metalloxyoxydimetall phosphine oxide)

Example 2-1 (Synthesis of 4-metalloxyoxyphenyl bromide)

Except for changing 551 g (7.2 mol) of allyl chloride used in Example 1-1 to 652 g (7.2 mol) of metalyl chloride, the procedure was the same as in Example 1-1, and about 4-metalyloxyphenylbromide was used. 1,500 g was prepared.

Example 2-2 (Synthesis of 4-metalloxyoxymagnesium halogenide)

200 g of 4-allyloxyphenyl bromide 32% tetrahydrofuran solution and 1,800 g of 4-allyloxyphenyl bromide 32% tetrahydrofuran solution used in Example 1-2 were added to 4-metalloxyoxy bromide 34% tetrahydrofuran solution. Except for changing to 200g and 1,800g of 34% tetrahydrofuran solution was carried out in the same manner as in Example 1-2 to prepare 4-metal aryloxyphenyl magnesium bromide.

Example 2-3 Synthesis of Metall Magnesium Chloride

Nitrogen gas was blown through a suction port into a 2,000 ml five-necked flask equipped with a stirrer, a thermometer, a reflux cooler, a dropping rod, and a gas inlet to replace air in the flask. 800 g of tetrahydrofuran, 87.6 g of metal magnesium, and 0.05 g of iodine were added thereto. The stirrer was operated to inject nitrogen gas into the gas inlet. The flask was kept at 40 ° C. and 271 g of metalyl chloride was added dropwise through a dropping rod. The dropping process was carried out for 3 hours and was intensive for 1 hour. Excess metal magnesium was removed and a tetrahydrofuran solution of metalylmagnesium chloride was prepared.

Example 2-4 Synthesis of 4-metalloxyoxydiphenoxyphosphine

Except for changing the amount of half of the 4-allyloxyphenylmagnesium bromide tetrahydrofuran solution prepared in Example 1-2 to half the amount of 4-metalloxyoxymagnesium bromide prepared in Example 2-2 In the same manner as in Example 1-3, 4-metalyloxyphenyldiphenoxyphosphine was prepared.

Example 2-5 (Synthesis of 4-metalloxyoxyphenyl dimetall phosphine)

Subsequent to Examples 2-4, the entire amount of the metalylmagnesium chloride tetrahydrofuran solution prepared in Example 2-3 from the dropping rod was added dropwise at a temperature of 20 to 30 ° C. for 1 hour, and it was recessed for 1 hour. . Thereafter, the same procedure as in Example 1-4 was carried out to prepare about 380 g of 4-metalloxyoxydimetall phosphine. This compound is ³¹ P { ¹ H} Confirmed by NMP and ¹ H NMR.

Example 2-6 (Synthesis of 4-Metalyloxyphenyldimetallylphosphine oxide)

The 4-metalyloxyphenyldimetallylphosphine prepared in Example 2-5 was oxidized and vacuum distilled in the same manner as in Example 1-5 to prepare about 320 g of 4-metalyloxyphenyldimetallylphosphine oxide. . The infrared absorption spectrum of the product is shown in Figure 4, ³¹ P { ¹ H} NMR is shown in FIG. 5 and ¹ H NMR is shown in FIG. 6. Elemental analysis showed that the carbon was 71.2% (theoretical value; 71.03%), hydrogen was 8.3% (theoretical value: 8.28%), and phosphorus was 10.2% (theoretical value: 10.18%). It was confirmed that the metal yl phosphine oxide.

Example 3 Synthesis of Tris- (4-allyloxyphenyl) phosphine

Nitrogen gas was blown through the gas inlet to replace the air in the flask with a liquid outlet at the bottom in an internal 5,000 ml glass 5-necked flask equipped with a stirrer, thermometer, reflux cooler, gas inlet and drip rod. To this, 700 g of toluene and 155 g (0.5 mol) of triphenylphosphite were injected. Half the amount of the 4-allyloxyphenylmagnesium bromide tetrahydrofuran solution obtained in Example 1-2 was added dropwise for 3 hours through a dropping rod at a temperature of 20 to 30 ° C. with stirring, and then intensively for 2 hours. . LC analysis confirmed that the obtained product was tris- (4-allyloxyphenyl) phosphine. 900 g of 10% sulfuric acid aqueous solution was added dropwise thereto for 30 minutes. It was left to stand for 30 minutes, stirring for 30 minutes here. 1,000 g of purified water was added thereto while the lower aqueous layer was removed, stirred for 30 minutes, and allowed to stand for 30 minutes. Again removing the water layer, tetrahydrofuran, toluene and phenol were distilled off under reduced pressure to prepare about 200 g of tris- (4-allyloxyphenyl) phosphine. This was dissolved in 400 g of methylene chloride, and cooled to -10 ° C to precipitate crystals. It was filtered, washed with 150 g of cooled methylene chloride, and dried to obtain about 170 g of white crystals. Infrared absorption spectrum of the product is shown in Figure 7, ³¹ P { ¹ H} NMR is shown in FIG. 8 and ¹ H NMR is shown in FIG. 9. From this result, it was confirmed that the product is tris- (4-allyloxyphenyl) phosphine.

Example 4 Synthesis of Tris- (4-allyloxyphenyl) phosphine oxide

43 g of tris- (4-allyloxyphenyl) phosphine prepared in Example 3 and acetic acid in a 300 ml glass four-necked flask equipped with a stirrer, thermometer, dropping rod and distillation cooler 150 g was injected. The flask was cooled with stirring to maintain the contents at 20 ° C. 113 g of 30% aqueous hydrogen peroxide solution was slowly added thereto via a dropping rod. The dropping process was carried out for 2 hours, and also recessed for 1 hour. 150 g of water and 50 g of dichloromethane were added to the reaction mixture, followed by stirring. Next, 150 g of water was added and the same operation was carried out, and tetrahydrofuran, toluene and water were completely removed by high vacuum distillation to obtain 45 g of a viscous liquid. Its infrared absorption spectrum is shown in Figure 10, ³¹ P { ¹ H} NMR is shown in Figure 11 and ¹ H NMR is shown in Figure 12. From these results, it was confirmed that the product is tris- (4-allyloxyphenyl) phosphine oxide.

Example 5 Synthesis of Tris- (4-allyloxyphenyl) phosphine oxide

A stirrer, thermometer, reflux condenser, gas inlet tube, and dropping inlet device were attached, and nitrogen gas was introduced into a 5,000 ml five-necked glass flask equipped with an outlet device at the bottom through a gas inlet to replace air in the flask. 700 g of toluene and 76.8 g (0.5 mol) of phosphorus oxychloride (POCl ₃ ) were added thereto. While stirring, the temperature of the contents was maintained at 80 to 110 ° C, and 1.5 mol of tetrahydrofuran solution of 4-allyloxyphenylmagnesium bromide obtained in the same manner as in Example 1-2 was added dropwise to the dropwise inlet for 6 hours. Boiling tetrahydrofuran was discharged from the bottom of the reflux condenser and then aged for 5 hours. The production of the target compound was confirmed by GC. 900 g of 10% sulfuric acid aqueous solution was added dropwise to the reaction mixture for 30 minutes, stirred for 30 minutes, and the lower aqueous layer was removed. 1,000 g of purified water was added again, and after stirring for 30 minutes, the aqueous layer was removed. Under high vacuum, tetrahydrofuran, toluene and a small amount of water were removed to give tris- (4-allyloxyphenyl) phosphine oxide, the same product as in Example 4.

Example 6 Synthesis of 3-allyl-4-hydroxyphenyldiallylphosphine oxide

150 g of 4-allyloxyphenyldiallylphosphine oxide prepared in Example 1-5 and 200 g of γ-butyrolactone were added thereto. The flask was heated to boil the contents while blowing nitrogen gas through the gas inlet. The temperature of the contents was 210 ° C., and it was confirmed by GC analysis that 6 hours later, it was converted to 3-allyl-4-hydroxyphenyldiallylphosphine oxide. After distilling gamma -butyrolactone under high vacuum and reduced pressure, 155 g of viscous liquid was obtained. Infrared absorption spectra are shown in Figure 13, ³¹ P { ¹ H}. NMR is shown in FIG. 14 and ¹ H NMR is shown in FIG. 15. From these results, it was confirmed that the obtained product is 3-allyl-4-hydroxyphenyl diallylphosphine oxide. The results of elemental analysis were the same as that of the isomer, 4-allyloxyphenyldiallylphosphine oxide.

Example 7 Synthesis of 3-Metalyl-4-hydroxyphenyldimetallylphosphine oxide

150 g of 4-metalloxyoxydimetall phosphine oxide prepared in Example 2-6 was treated in the same manner as in Example 6 to obtain about 160 g of a viscous compound. Infrared absorption spectrum is shown in Figure 16, ³¹ P { ¹ H} NMR is shown in FIG. 17 and ¹ H NMR is shown in FIG. From these results, it was confirmed that the obtained product is 3-metall-4-hydroxyphenyl dimetall phosphine oxide.

Example 8 Synthesis of Tris- (3-allyl-4-hydroxyphenyl) phosphine oxide

Into a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, and a gas inlet, 150 g of tris- (4-allyloxyphenyl) phosphine oxide obtained in Example 4 or 5 and 100 g of gamma butyl lactone were added thereto. The temperature of the contents was maintained at 180 ° C while slowly introducing nitrogen gas from the. After about 5 hours the completion of the intramolecular transfer reaction was confirmed by liquid chromatography (HPLC) analysis. 500 g of toluene was added to the contents to melt, and then cooled slowly to precipitate crystals. The crystals were filtered off, washed with 100 g of toluene and dried to obtain 130 g of white crystals. The obtained product had a melting point of 260 ° C., infrared absorption spectra of FIGS. 19, ³¹ P { ¹ H} NMR, and FIG. 20 and ¹ H NMR of FIG. 21, and the resulting product was tris- (3-allyl. It was confirmed that it is 4-hydroxyphenyl) phosphine oxide. At this time, deuterium substituted dimethyl sulfoxide (D ₆ -DMSO) was used as the NMR solvent.

(Example 9)

10% of 4-allyloxyphenyldiallylphosphine oxide obtained in Example 1 was added to XYLON (a mixture of polystyrene and polyphenylene oxide) manufactured by Asahi Kasei Co., Ltd. Pellets were prepared in a Model TEN-37BS test extrusion machine. The prepared pellets were again made into a test piece having a thickness of 1/8 inch conforming to UL-94 standard using an extrusion molding machine. Some of the test pieces were irradiated with γ-ray of cobalt 60 for 20 seconds. The gamma-irradiation treated test piece and the untreated test piece were deposited for 10 seconds in a lead bath heated to 320 ° C. The former had little change, while the latter was remarkably modified. As a result, the effect by gamma irradiation was confirmed. In the test conducted by the UL-94 flame retardancy test method, both exhibited flame retardancy corresponding to V-0.

(Comparative Example 1)

A test piece having a thickness of 1/8 inch was prepared in accordance with the standard of UL-94 using the XYLON used in Example 9 as an extruder. A part of them was irradiated with gamma rays of cobalt 60 for 20 seconds. The test γ of the gamma ray irradiation treatment and the untreated test piece were immersed in a solder bath heated to 320 ° C. for 10 seconds, but both were deformed in the same manner, and the effect of the gamma ray irradiation treatment was not found. In addition, in the test according to the flame retardancy method of UL-94, both exhibited flame retardancy corresponding to V-2.

From this result and the result of Example 9, it was confirmed that 4-allyloxy phenyl diallyl phosphine oxide has the function as a PFM and a flame retardant with respect to polycarbonate.

(Example 10)

A test piece was prepared by treating XYLON used in Example 9 with 12% of 4-metalloxyoxydimetall phosphine oxide obtained in Example 2 and mixing the same as in Example 9. The gamma-ray irradiation treated test piece and the untreated test piece were deposited for 10 seconds in a solder bath heated to 320 ° C. The former had little change, while the latter was remarkably modified. Therefore, the effect by gamma irradiation was confirmed. In addition, in the test according to the flame retardancy test method of UL-94, the former shows flame retardancy corresponding to V-0.

From this result and the result of the comparative example 1, it was confirmed that 4-metalyloxy phenyl dimetallyl phosphine oxide contains the function as PFM and the function as a flame retardant with respect to XYLON.

(Example 11)

10% of 3-allyl-4-hydroxyphenyl diallyl phosphine oxide obtained in Example 6 was added to 6,6-nylon made by Nippon Chemical Co., Ltd. and manufactured according to UL-94 standard. A 1/8 inch test piece was prepared. Some of the test pieces were irradiated with gamma rays of cobalt 60 for 20 seconds. The test piece and the untreated test piece of the gamma ray irradiation treatment were deposited for 10 seconds in a solder bath heated to 320 ° C. The former had little change, while the latter changed significantly. Therefore, the effect by gamma irradiation was confirmed. In addition, in the test according to the UL-94 flame retardancy test method, the former showed a flame retardancy corresponding to V-1.

(Comparative Example 2)

The 6,6-nylon used in Example 11 was extruded as it was, and the test piece of thickness 1/8 inch corresponding to the specification of UL-94 was created. A part of them was irradiated with gamma rays of cobalt 60 for 20 seconds. The test piece and the untreated test piece of the γ-ray irradiation treatment were immersed in a solder bath heated to 320 ° C. for 10 seconds. In addition, in the test according to the flame retardancy test method of UL-94, both were burned in the same manner and did not exhibit flame retardancy.

From this result and the result of Example 11, it was verified that 3-allyl-4-hydroxyphenyl diallyl phosphine oxide has the function as a PFM and a flame retardant with respect to 6, 6- nylon.

(Example 12)

To 6,6-nylon, 11% of 3-metall-4-hydroxyphenyldimetallylphosphine oxide obtained in Example 6 was added and mixed, and the test piece was prepared in the same manner as in Example 9. Some of the test pieces were irradiated with gamma rays from cobalt 60 for 20 seconds. The test piece and the untreated test piece of the gamma ray irradiation treatment were deposited for 10 seconds in a solder bath heated to 320 ° C. The former did not change at all, while the latter changed significantly. Thereby, the effect by gamma-ray irradiation was confirmed. In addition, in the test according to the flame retardancy test method of UL-94, the former showed flame retardancy corresponding to V-1. From the result and the result of the comparative example 2, it was verified that 3-metall- 4-hydroxyphenyl dimetall phosphine oxide contains the function as a PFM and a function as a flame retardant.

(Example 13)

12% of tris- (3-allyl-4-hydroxyphenyl) phosphine oxide obtained in Example 8 was added to 6,6-nylon and mixed to prepare a test piece in the same manner as in Example 11. Some of them were irradiated with gamma rays from cobalt 60 for 20 seconds. The test piece and the untreated test piece of the gamma ray irradiation treatment were deposited for 10 seconds in a solder bath heated to 320 ° C. The former was not modified at all, while the latter was markedly modified. Thereby, the result by gamma irradiation was confirmed. In the test according to the flame retardancy test method of UL-94, the latter showed the flame retardancy of V-1. From the results and the results of Comparative Example 2, it was verified that the tris- (3-allyl-4-hydroxyphenyl) phosphine oxide includes a function as a PFM and a function as a flame retardant.

(Example 14)

Tris- (3-allyl-4-hydroxyphenyl) obtained in Example 6 in 100 parts of an epoxy resin mainly containing 2,2-bis- (4-glycidyloxyphenyl) propane manufactured by Korea and Kukdo Chemical. 45 parts of phosphine oxides were added, mixed well, and reacted at 100 degreeC for 5 hours. 10 parts of dicyandiamide was added here, and also hardening reaction was performed at 120 degreeC for 5 hours, and the cured epoxy resin which has high heat resistance was obtained. From this, the test piece of thickness 1/8 inch which conforms to UL-94 standard was deposited. The combustion test of the test piece showed the flame retardancy of V-0. As a result, it was proved to include the function as a hardening | curing agent and a function as a flame retardant of a tris- (3-allyl-4-hydroxyphenyl) phosphine oxide epoxy resin.

(Reference Example 1)

The following experiment was conducted for the purpose of verifying the non-hydrolyzability of the functional organophosphorus compound of the present invention. 4-allyloxyphenyldiallylphosphine oxide obtained in Examples 1 to 8, 4-metalyloxyphenyldimetallylphosphine oxide, and tris- (4-allyloxyphenyl) in 100 g of methanol solution of 30% potassium hydroxide. Phosphine, tris- (4-allyloxyphenyl) phosphine oxide, 3-allyl-4-hydroxyphenyl diallyl phosphine oxide, 3-metall-4-hydroxyphenyl dimetall phosphine oxide, tris To compare with-(3-allyl-4-hydroxyphenyl_phosphine oxide, 10 g of each of commercially available triphenylphosphate (triphenyl phosphate) and commercial triallyl phosphate (triallyl phosphate) were added, respectively, in methanol boiling state. The change was investigated by LC analysis, and no change was observed in the functional organophosphorus compounds of Examples 1 to 8, but triphenylphosphate was diphenylphosphate and phenol, and triallyl phosphate was diallyl phosphate. Completely hydrolyzed to allyl alcohol, provided that potassium hydroxide and salts were thought to form salts, but LC analysis could not identify them.

The functional organophosphorus compounds of the present invention can all be easily produced on an industrial scale, are non-hydrolyzable, and very stable even when added to organic molecules as a flame retardant. In addition, the functional organophosphorus compound having no hydroxy group has a function of flame retardant polyfunctional monomer (PFM) for the mixture of polystyrene and polyphenylene oxide, and the functional organophosphorus compound having hydroxy group is flame retardant PFM for 6,6-nylon. Has the function of

Moreover, the functional organophosphorus compound which has three hydroxyl groups has both a function as a hardening | curing agent and a function as a flame retardant with respect to an epoxy resin. Such results indicate the industrial utility of the present invention.

Claims (26)

A functional organophosphorus compound represented by the following Formula 1 and containing three unsaturated groups in the molecule. [Formula 1]

(In Formula 1, R ¹ represents a 4-allyloxyphenyl group, 4-metalloxyphenyl group, 3-allyl-4-hydroxyphenyl group, or 3-metalloxyoxyhydroxy group, and R ² and R ³ represents the same or independently of each other an allyl group, metalyl group, 4-allyloxyphenyl group, 4-metalyloxyphenyl group, 3-allyl-4-hydroxyphenyl group or 3-metalyl-4-hydroxyphenyl group , n represents 0 or 1.) The functional organophosphorous compound according to claim 1, wherein R ¹ is a 4-allyloxyphenyl group, R ² and R ³ are allyl groups, and n is 1. 4. The functional organophosphorus compound according to claim 1, wherein R ¹ is a 4-metalyloxyphenyl group, R ² and R ³ are metalyl groups, and n is 1. 4. The functional organophosphorous compound according to claim ¹ , wherein R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, and n is 0. The functional organophosphorous compound according to claim ¹ , wherein R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, and n is 1. 2. The functional organophosphorous compound of claim 1, wherein R ¹ is a 3-allyl-4-hydroxyphenyl group, R ² and R ³ are allyl groups, and n is 1. The functional organophosphorous compound according to claim 1, wherein R ¹ is a 3-metalyl-4-hydroxyphenyl group, R ² and R ³ are metalyl groups, and n is 1. 4. The functional organophosphorous compound of claim ¹ , wherein R ¹ , R ^2, and R ³ are 3-allyl-4-hydroxydiphenyl groups, and n is 1. Functionality of the formula (1) comprising the step of condensation reaction of the organophosphorus compound of formula (2) with the Grignard reagent represented by RMgX (R is C ₂ to C ₈ alkyl group, C ₆ to C ₁₄ allyl group, X is halogen) Process for the preparation of organophosphorus compounds. [Formula 1]

[Formula 2]

(In the above formulas (1) and (2), R ¹ represents a 4-allyloxyphenyl group or a 4-metalloxyphenyl group, and R ² and R ³ are the same or independently of each other, an allyl group, metalyl group, 4-allyloxyphenyl group). , 4-metalyloxyphenyl group, 3-allyl-4-hydroxyphenyl group or 3-metalyl-4-hydroxyphenyl group, n represents 0 or 1, R ⁴ represents a 4-allyloxyphenyl group or a 4-metallyloxyphenyl group, X is a chlorine atom, bromine atom or phenoxy group and m represents 0 or 1.) 10. The method according to claim 9, wherein the Grignard reagent is allyl magnesium halogenide, metalylmagnesium halogenide, 4-allyloxyphenylmagnesium halogenide and 4-metallyloxy phenylmagnesium halogenide. Method for producing a functional organophosphorus compound selected from the group consisting of. 10. The compound of claim 9, wherein R ⁴ is an allyloxyphenyl group, X is a phenoxy group, a chlorine atom or a bromine atom, and m is 0. Wherein the Grignard reagent is 4-allyloxyphenylmagnesium halogenide. 10. The method of claim 9, wherein the Grignard reagent is allyl magnesium halogenide, metalyl magnesium halogenide or allyloxyphenyl magnesium halogenide, wherein R ¹ is a 4-allyloxyphenyl group, R ² and R ^Tri is an allyl group; R ¹ is a metalyloxyphenyl group, R ² and R ³ are metalyl groups; Or R ¹ , R ² and R ³ are 4-allyloxyphenyl groups, n is 1, and a method for producing a functional organophosphorus compound. The method for producing a functional organophosphorous compound according to claim 9, wherein m is 0 and an oxidation reaction is further performed using an oxidizing agent. A condensation reaction of an organophosphorus compound of Formula 2 with a Grignard reagent represented by RMgX (R is a C ₂ to C ₈ alkyl group, a C ₆ to C ₁₄ allyl group, X is a halogen); Process for producing a functional organophosphorus compound of the formula (1) to perform the intramolecular transition reaction of the condensation product.   [Formula 1]

[Formula 2]

(In the above formulas 1 and 2, R ¹ represents a 3-allyl-4-hydroxyphenyl group or a 3-metalyloxy-4-hydroxyphenyl group, R ² and R ³ are the same or independently of each other an allyl group , A metalyl group, 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group, or 3-metall-4-hydroxyphenyl group, n represents 0 or 1, R ⁴ represents a 4-allyloxyphenyl group or a 4-metallyloxyphenyl group, X is a chlorine atom, bromine atom or phenoxy group and m represents 0 or 1.) The method for producing a functional organophosphorous compound according to claim 9, wherein an oxidation reaction is further performed after the condensation reaction. delete The method of claim 9, wherein the organic phosphorus compound of Formula 2 A method for producing a functional organophosphorous compound, which is prepared by condensation reaction of a Grignard reagent with one selected from the group consisting of phosphorus trihalide, phosphite compounds and phosphorus oxychloride. 1 mole of phosphite compound or phosphorus oxychloride selected from the group consisting of phosphorus trihalide, triphenyl phosphite (triphenyl phosphite), tricresyl phosphite, monocresyl diphenyl phosphite and dicresyl monophenyl phosphite; A process for preparing a functional organophosphorous compound of formula 1 including the step of condensing 3 moles of Grignard reagent represented by RMgX (wherein R is a C ₂ to C ₈ alkyl group, a C ₆ to C ₁₄ allyl group, and X is a halogen) . [Formula 1]

(In Formula 1, R ¹ represents a 4-allyloxyphenyl group or a 4-metalloxy phenyl group, R ² and R ³ are the same or independently of each other an allyl group, metalyl group, 4-allyloxyphenyl group, 4 -Metalloxyoxy group, 3-allyl-4-hydroxyphenyl group, or 3-metall-4-hydroxyphenyl group, n represents 0 or 1) 19. The method for producing a functional organophosphorous compound according to claim 18, wherein an oxidation reaction is further performed after condensation of the phosphorus trihalide or phosphite compound with the Grignard reagent. 4-allyloxyphenyldiallylphosphine oxide, 4-metalloxyoxydimetallylphosphine oxide, tris- (4-allyloxyphenyl) phosphine and tris- (4-allyloxyphenyl) phosphine oxide A method for producing a flame-retardant, heat-resistant polycarbonate molded article comprising the step of irradiating a polystyrene-polyphenyl dioxide resin molded article containing 1 to 25% by weight of a functional organophosphorous compound selected from the group. The method for producing a flame-retardant, heat-resistant polycarbonate molded article according to claim 20, wherein the organophosphorus compound is 4-allyloxyphenyldiallylphosphine oxide or 4-metallyloxyphenyldimetallyl phosphine oxide. 3-allyl-4-hydroxyphenyldiallylphosphine oxide, 3-metall-4-hydroxyphenyldimetallylphosphine oxide, tris- (3-allyl-4-hydroxyphenyl) phosphine and tris- Flame-retardant, heat-resistant polyamide comprising a step of irradiating a polyamide molded article comprising 2 to 25% by weight of a functional organophosphorous compound selected from the group consisting of (3-allyl-4-hydroxyphenyl) phosphine oxide Method for producing a molded article. 23. The method of claim 22, wherein the functional organophosphorus compound is 3-allyl-4-hydroxyphenyldiallylphosphineoxide, 3-metalyl-4-hydroxyphenyldimetallylphosphine oxide and tris (3-allyl- A method of producing a flame-retardant, heat-resistant polyamide molded article comprising the step of irradiating a polyamide molded article comprising 2 to 25% by weight of a functional organophosphorus compound selected from the group consisting of 4-hydroxyphenyl) phosphine oxide. Flame retardant epoxy resin composition comprising 10 to 40% by weight of the functional organophosphorus compound of the formula (1). [Formula 1]

(In Formula 1, R ¹ represents a 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group, or 3-metallyloxy-4-hydroxyphenyl group, and R ² and R ³ represents the same or independently of each other an allyl group, metalyl group, 4-allyloxyphenyl group, 4-metalyloxyphenyl group, 3-allyl-4-hydroxyphenyl group or 3-metalyl-4-hydroxyphenyl group , n represents 0 or 1) The flame retardant epoxy resin composition according to claim 24, wherein the functional organophosphorus compound is tris- (3-allyl-4-hydroxyphenyl) phosphine oxide. 1 mole of phosphite compound or phosphorus oxychloride selected from the group consisting of phosphorus trihalide, triphenyl phosphite (triphenyl phosphite), tricresyl phosphite, monocresyl diphenyl phosphite and dicresyl monophenyl phosphite; Condensation of 3 moles of Grignard reagent represented by RMgX (wherein R is a C ₂ to C ₈ alkyl group, a C ₆ to C ₁₄ allyl group, X is a halogen); Method for producing a functional organophosphorus compound of formula 1 comprising the step of performing an intramolecular transition reaction of the condensation product. [Formula 1]

(In Formula 1, R ¹ represents a 3-allyl-4-hydroxyphenyl group or a 3-metalyloxy-4-hydroxyphenyl group, R ² and R ³ are the same or independently of each other an allyl group, metal A aryl group, 4-allyloxyphenyl group, 4-metalloxyoxy group, 3-allyl-4-hydroxyphenyl group, or 3-metall-4-hydroxyphenyl group, n represents 0 or 1)

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