JP2006069980A - Functional organophosphorus compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional organophosphorus compound which is a non-hydrolyzable organophosphorus compound having a plurality of unsaturated groups in its molecule, having a flame retardant function for an organic polymeric compound and a function as a cross-linking agent jointly, since the cross-links are formed between the organic polymer compounds by treating with a radiation such as an electron beam or γ-ray, and also useful as a raw material for an organic synthesis, use of the same and also a method for producing the same. <P>SOLUTION: This functional organophosphorus compound is expressed by general formula 1 [wherein, R<SP>1</SP>and R<SP>2</SP>are each a 4-allyloxyphenyl, 3-allyl-4 hydroxyphenyl or 3-metallyl-4-hydroxyphenyl group; and R<SP>3</SP>is a 1-7C hydrocarbon, 3-allyl-4-hydroxyphenyl or 3-metallyl-4-hydroxyphenyl group] and having a plurality of unsaturated groups in its molecule. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a functional organophosphorus compound. More specifically, it is a non-hydrolyzable organophosphorus compound having a plurality of unsaturated groups in the molecule, and is treated with radiation such as an electron beam or gamma ray to form an organic polymer compound. As a result of the formation of crosslinks, functional organic phosphorus compounds that have both the function as a flame retardant of an organic polymer compound and the function as a crosslinker, and are useful as raw materials for organic synthesis. The present invention relates to a compound, its use, and its production method.

  Organophosphorus compounds are useful as stabilizers, plasticizers or flame retardants for organic polymer compounds, and have a wide range of uses as special surfactants, extreme pressure additives, or agricultural chemicals. Among these, as flame retardants for polymer compounds, organic halogen compounds that have been used for the same purpose generate toxic gases during combustion in fires, corrode incinerators during incineration, and environmentally hazardous substances. In the industry that uses flame retardants, there is an active movement to replace halogen-based flame retardants with other flame retardants. Attention has been paid.

  However, most of the organophosphorus compounds that have been used as flame retardants in the past are phosphoric acid ester-based compounds, which are more easily hydrolyzed than organic halogen compounds, especially for applications such as electrical parts or electronic equipment parts. For the purpose of maintaining electrical insulation, there is a strong demand for non-hydrolyzable organic phosphorus compounds. Conventionally, phosphate-based organophosphorus compounds that have been widely used are hydrolyzed in the presence of high-temperature moisture or alkali in the polymer material, and the product reduces the electrical insulation of the polymer material. Or, in extreme cases, there is a tendency to corrode fine electrical wiring provided on a substrate made of a polymer material. Therefore, it is a problem when these flame retardants are used in applications such as electrical parts or electronic equipment parts, and the development of non-hydrolyzable organophosphorus compounds is an urgent need, and it is awaited. Is the current situation.

  On the other hand, it has a plurality of unsaturated groups and has a function capable of forming a crosslinking bond with a polymerization or organic polymer compound by treatment with a polymerization initiator or radiation such as ultraviolet rays, electron beams or γ rays. The development of organophosphorus compounds possessed is also desired. Conventionally, in the manufacture of mechanical parts, electrical parts or electronic equipment parts that require high heat resistance, thermosetting materials with excellent heat resistance such as phenol resin, melamine resin, unsaturated polyester resin or epoxy resin are used. Resins have been used, but the disadvantages of using these thermosetting resins are: 1. Compared to the molding of thermoplastic resins. 1. It takes time to cure and the productivity is poor. 2. There is a limit to miniaturization or precision of parts; Product uniformity was not enough. Therefore, instead of these thermosetting resins, a thermoplastic resin molded product to which a crosslinking agent has been added is subjected to radiation treatment such as electron beams and γ rays to form a crosslinked structure in the resin and thermoset. Technology to provide heat resistance equivalent to that of functional resins has been developed and has already been put into practical use. Recently, there has been a demand for a crosslinking agent having a function as a flame retardant, and for this reason, development of an organophosphorus compound having a function as a crosslinking agent is also required. . According to this technique, for example, a self-crosslinking thermoplastic resin by radiation treatment such as polyethylene or some rubbers is crosslinked only by treatment with radiation or the like, and heat resistance is obtained without the presence of a crosslinking agent. Although some are known, many thermoplastic resins that are not self-crosslinkable, such as polypropylene, polystyrene, polycarbonate resin, polyphenylene oxide resin or polyamide resin, are usually used as crosslinkers prior to radiation treatment. Parts are formed after the addition of an organic compound called PFM (polyfunctional monomer), and then radiation such as electron beam or γ-ray is processed. Desired heat resistance is provided without changing the outer shape at all. PFM (hereinafter, a crosslinking agent for the purpose of radiation treatment is simply referred to as PFM) is an organic compound having a plurality of unsaturated groups, and is compatible with the target thermoplastic resin. There must be something. If the organophosphorus compound has a plurality of unsaturated groups, it can be expected to have both a function as a flame retardant and a function as a PFM. As such an organophosphorus compound, triallyl phosphate (triallyl phosphate) is well known at present, but this technology has low molecular weight and is volatile, and is easily hydrolyzed. It is only used for limited purposes. A flame-retardant PFM made of a non-hydrolyzable organophosphorus compound compatible with this technology is currently waiting for development.

In addition, non-hydrolyzable organophosphorus compounds having a plurality of phenolic hydroxy groups are valuable as epoxy resin curing agents for use in electrical parts or electronic equipment parts (see, for example, Patent Document 1). ), And the development is awaited as well.
JP 2000-186186 A

  As already explained, non-hydrolyzable compounds are required for organophosphorus compounds as flame retardants used particularly for electrical parts and electronic equipment parts. It is a first object of the present invention to provide a non-hydrolyzable organophosphorus compound. On the other hand, the development of a flame retardant PFM in which an organophosphorus compound has a plurality of unsaturated groups is desired. Providing such a functional organophosphorus compound is a second problem. Furthermore, it is also desirable that various uses and other useful organophosphorus compounds are derived from the reactivity of unsaturated groups or hydroxy groups possessed by functional organophosphorus compounds. The third issue. And it is the 4th subject to provide the industrial manufacturing method of such a functional organophosphorus compound.

  According to the present invention, a novel functional organophosphorus compound represented by the general formula 1, its use, and its production method are provided.

（式１中、Ｒ¹ およびＲ² は４−アリロキシフェニル基、３−アリル−４−ヒドロキシフェニル基または３−メタリル−４−ヒドロキシフェニル基を示し、Ｒ³ は１ないし７の炭素数を持っている炭化水素基、３−アリル−４−ヒドロキシフェニル基または３−メタリル−４−ヒドロキシフェニル基を示す。）
一般式１で表される機能性有機りん化合物ではりん原子と三個の炭素原子がすべて直接に結合している。この構造から理解されるように、これは非加水分解性であり、本発明の第一の課題が解決される。また、一般式１で表される有機りん化合物はすべてが複数個の不飽和基を持っていて、重合開始剤や放射線などの処理によって重合反応ないし有機高分子化合物に対しての架橋形成反応などの機能があり、難燃性ＰＦＭとしての第二の課題が解決される。さらに、この不飽和基は反応性に富んでいて酸化剤による酸化反応ではエポキシ化合物が、そのハロゲン化反応ではハロゲン化合物が誘導される。そして、一般式１で表される有機りん化合物の一部が持っているヒドロキシ基もまた反応性に富んでいて、有機ハロゲン化物とアルカリの存在下にエーテル化反応が容易に実施出来る。エーテル化反応の中で重要なのはグリシジルエーテル化反応である。ヒドロキシ基を持っている機能性有機りん化合物の内、ジ−（３−アリル−４−ヒドロキシフェニル）メチルホスフィンオキサイドなどは二個の、トリス−（３−アリル−４−ヒドロキシフェニル）ホスフィンオキサイドなどは三個のヒドロキシ基を持っていて、エポキシ樹脂の難燃性硬化剤としての機能を持つとともに、アルカリの存在下でエピハロヒドリンと縮合反応してグリシジルエーテルを形成して、ジ−（３−アリル−４−グリシジルオキシフェニル）メチルホスフィンオキサイドまたはトリス−（３−アリル−４−グリシジルオキシフェニル）ホスフィンオキサイドなどが得られる。これらには非加水分解性である特性が保持されていて、電気部品または電子機器部品の用途への難燃性エポキシ樹脂組成物として有用である。さらに、ヒドロキシ基のオルソ位置も反応性であって、ホルムアルデヒドなどと反応して難燃性のフェノール樹脂が誘導される。これらの一部の実例からも理解される通り、これらはさらに多くの誘導体への可能性を持っていて、第三の課題に答える事が出来る。

(In Formula 1, R ¹ and R ² represent a 4-allyloxyphenyl group, a 3-allyl-4-hydroxyphenyl group, or a 3-methallyl-4-hydroxyphenyl group, and R ³ represents 1 to 7 carbon atoms. It represents a hydrocarbon group, 3-allyl-4-hydroxyphenyl group or 3-methallyl-4-hydroxyphenyl group.)
In the functional organophosphorus compound represented by the general formula 1, the phosphorus atom and all three carbon atoms are directly bonded. As can be seen from this structure, it is non-hydrolyzable and solves the first problem of the present invention. In addition, all of the organophosphorus compounds represented by the general formula 1 have a plurality of unsaturated groups, and a polymerization reaction or a cross-linking reaction to an organic polymer compound is caused by treatment with a polymerization initiator or radiation. The second problem as a flame-retardant PFM is solved. Furthermore, this unsaturated group is rich in reactivity, and an epoxy compound is induced in the oxidation reaction with an oxidizing agent, and a halogen compound is induced in the halogenation reaction. The hydroxy group possessed by a part of the organophosphorus compound represented by the general formula 1 is also highly reactive, and the etherification reaction can be easily carried out in the presence of an organic halide and an alkali. An important etherification reaction is a glycidyl etherification reaction. Among functional organophosphorus compounds having a hydroxy group, di- (3-allyl-4-hydroxyphenyl) methylphosphine oxide and the like are two, tris- (3-allyl-4-hydroxyphenyl) phosphine oxide and the like Has three hydroxy groups and functions as a flame retardant curing agent for epoxy resins, and forms a glycidyl ether by condensation reaction with epihalohydrin in the presence of alkali to form di- (3-allyl). -4-Glycidyloxyphenyl) methylphosphine oxide or tris- (3-allyl-4-glycidyloxyphenyl) phosphine oxide is obtained. These retain their non-hydrolyzable properties and are useful as flame retardant epoxy resin compositions for electrical or electronic device applications. Furthermore, the ortho position of the hydroxy group is also reactive, and reacts with formaldehyde or the like to induce a flame retardant phenol resin. As can be seen from some of these examples, they have the potential for more derivatives and can answer the third challenge.

  The fourth problem is to provide an industrial production method of the functional organophosphorus compound of the present invention, which is solved by the method described below.

  Among the organophosphorus compounds represented by the general formula 1, those having no hydroxy group in the molecule, such as di- (4-allyloxyphenyl) methylphosphine oxide, are generally the same as the organophosphorus compounds represented by the general formula 2. It can be produced by subjecting a substituted magnesium halide represented by Formula 3 to a condensation reaction and, if necessary, an oxidation reaction.

（式２中、Ｒ⁴ は１ないし７の炭素数を持っている炭化水素基を示し、ｎは０または１を示す。）

(In formula 2, R ⁴ represents a hydrocarbon group having 1 to 7 carbon atoms, and n represents 0 or 1)

（式３中、Ｒ⁵ は４−アリロキシフェニル基または４−メタリロキシフェニル基を示し、Ｘは塩素原子または臭素原子を示す。）
一般式１で表される有機りん化合物の内、分子内に二個のヒドロキシ基を持っているジ−（３−アリル−４−ヒドロキシフェニル）メチルホスフィンオキサイドなどは上記の製造方法で得られた分子中にヒドロキシ基を持っていない有機りん化合物の分子内転移反応によって製造する事が出来る。

(In Formula 3, R ⁵ represents a 4-allyloxyphenyl group or a 4-metalryloxyphenyl group, and X represents a chlorine atom or a bromine atom.)
Among the organophosphorus compounds represented by the general formula 1, di- (3-allyl-4-hydroxyphenyl) methylphosphine oxide having two hydroxy groups in the molecule was obtained by the above production method. It can be produced by an intramolecular transfer reaction of an organophosphorus compound having no hydroxy group in the molecule.

  Among the organophosphorus compounds represented by general formula 1, tris- (3-allyl-4-hydroxyphenyl) phosphine oxide and tris- (3-methallyl-4-hydroxyphenyl) phosphine oxide are represented by general formula 3. Tris- (4-allyloxyphenyl) phosphine oxide or tris obtained by subjecting the substituted magnesium halide to a condensation reaction with phosphorus trichloride, triphenyl phosphite or phosphorus oxychloride and, if necessary, an oxidation reaction It can be produced by causing an intramolecular transfer reaction to-(4-metalloxyphenyl) phosphine oxide.

  As is clear from each example, it has been confirmed that any of the functional organophosphorus compounds of the present invention can be produced on an industrial scale, and it is clear from the results of each example, comparative example and reference example. In addition, it has been demonstrated that it is non-hydrolyzable and is extremely stable even when added to an organic polymer compound as a flame retardant. A functional organophosphorus compound having no hydroxy group has a flame retardant PFM function for a mixture of polystyrene and polyphenylene oxide, and a functional organophosphorus compound having a plurality of hydroxy groups is an epoxy. It was confirmed that the resin has both a function as a curing agent and a function as a flame retardant. Furthermore, it was confirmed that the functional organophosphorus compound having a plurality of hydroxy groups and a plurality of unsaturated groups has thermal reactivity with epoxy resins and crosslinking reactivity with γ rays. These results show the industrial utility of the present invention.

  According to the present invention, there is provided a non-hydrolyzable functional organophosphorus compound represented by the general formula 1 and having a plurality of unsaturated groups in the molecule, its use and its production method.

  Hereinafter, although this invention is demonstrated, illustrating the more preferable embodiment of the functional organophosphorus compound of this invention, its use, and its manufacturing method, this does not limit invention.

  By subjecting the organophosphorus compound represented by the general formula 2 to the condensation reaction of the substituted magnesium halide represented by the general formula 3, the organophosphorus compound represented by the general formula 4 is produced.

（式４中、Ｒ⁴ は一般式２の定義と同じであり、Ｒ⁵ は一般式３の定義と同じであり、ｎは０または１を示す。）
一般式４で表される有機りん化合物はすべてが分子中にヒドロキシ基を持っていないものであり、必要ならば酸化反応を行なわせる事によって一般式４のｎが１である有機りん化合物に変換される。一般式１で表される機能性有機りん化合物の内、分子内にヒドロキシ基を持っていないものは一般式４に含まれている。

(In formula 4, R ⁴ has the same definition as in general formula 2, R ⁵ has the same definition as in general formula 3, and n represents 0 or 1.)
All of the organophosphorus compounds represented by the general formula 4 have no hydroxy group in the molecule, and if necessary, they are converted into organophosphorus compounds in which n in the general formula 4 is 1 by performing an oxidation reaction. Is done. Among the functional organophosphorus compounds represented by general formula 1, those having no hydroxy group in the molecule are included in general formula 4.

  Among functional organophosphorus compounds represented by general formula 1, those having two hydroxy groups in the molecule undergo intramolecular transfer reaction to organophosphorus compounds in which n in general formula 4 is represented by 1. It can be manufactured by doing it.

  Examples of the organic phosphorus compound represented by the general formula 2 include methyldichlorophosphine, methyldichlorophosphine oxide, ethyldichlorophosphine oxide, n-butyldichlorophosphine, n-butyldichlorophosphine oxide, tertiarybutyldichlorophosphine oxide, allyldichlorophosphine, Allyldichlorophosphine oxide, phenyldichlorophosphine, phenyldichlorophosphine oxide, benzyldichlorophosphine, benzyldichlorophosphine oxide, and the like are known. Some of these organophosphorus compounds can be commercially available, while others can be produced by known synthesis methods.

  These condensation reactions are well-known personal name reactions called Gregnard reactions. Substituted magnesium halides such as 4-allyloxyphenylmagnesium halide or 4-metalryloxyphenylmagnesium halide are called “Gregnard reagent”, and the reaction between an organic halogen compound and metal magnesium. Prepared by Usually, the preparation of the Grineer reagent is carried out in the presence of anhydrous ethyl ether or tetrahydrofuran (hereinafter referred to as THF). However, at present, ethyl ether is rarely used, and THF is almost used. Also in the present invention, it is preferable to prepare a Grineer reagent and perform a Grineer reaction using THF.

  The preparation of the Grineer reagent related to the present invention can be achieved by reacting the corresponding substituted halogenide with magnesium metal in the presence of THF. If a small amount of iodine is present at the beginning, the reaction is smooth. Of 4-allyloxyphenyl halide and 4-metalloxyphenyl halide, 4-allyloxyphenyl chloride and 4-metalloxyphenyl chloride are extremely slow to react with magnesium metal, and under pressure It only progresses at higher temperatures. Therefore, it is convenient and recommended to use these bromides in the preparation of Grineer reagents in the laboratory.

  4-Allyloxyphenyl halogenide or 4-metalloxyphenyl halide is an alkali-containing 4-hydroxyphenyl chloride (parachlorophenol) or 4-hydroxyphenyl bromide (parabromophenol) and allyl chloride or methallyl chloride. It is prepared by conducting a condensation reaction in the presence. Sodium hydroxide and potassium hydroxide are used as the alkali, but sodium hydroxide is economical and preferred. In addition, parachlorophenol is produced by chlorination of phenol with chlorine or sulfuryl chloride, but in chlorination with chlorine, many orthochlorophenols are by-produced and yield is poor, and chlorination with sulfuryl chloride is carried out. . Parabromophenol is produced by bromination of phenol with bromine, but bromination at low temperatures is preferred because fewer by-products such as orthobromophenol are produced.

  Among the organophosphorus compounds represented by the general formula 1, those having three hydroxy groups in the molecule are 4-allyloxyphenylmagnesium halide or 4-metalryloxyphenylmagnesium halide and phosphorus trichloride. , Triphenyl phosphite or phosphorus oxychloride can be subjected to a condensation reaction, and if necessary, an oxidation reaction can be carried out, followed by an intramolecular transfer reaction.

  Usually, the Grineer reaction is carried out in the presence of an anhydrous inert organic solvent. Inert organic solvents include ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), dioxane, pyran, n-hexane, heptane, nonane, decane, cyclohexane, benzene, toluene, xylene, trimethylbenzene or Examples include ethylbenzene.

  The inert organic solvent after the condensation reaction contains magnesium halide formed by the condensation reaction in addition to the target compound. If water or dilute acid is added to this and washed with water, inorganic salts are removed and the produced organic phosphorus compound is separated. If the organic solvent contained therein is removed by distillation, the phosphines or phosphine oxides are concentrated.

  The intramolecular transfer reaction is called “Claisen rearrangement” and is also famous as a personal name reaction. This transfer reaction can be achieved by simply heating to 150 to 250 ° C., but is accelerated by the addition of a Lewis acid such as magnesium chloride, aluminum chloride, zinc chloride, ferric chloride or an acidic catalyst such as sulfuric acid or sulfonic acid. . The transfer reaction is an exothermic reaction, and it is preferable to carry out the reaction in an inert solvent for the purpose of mild and smooth reaction. As inert solvents, hydrocarbons such as heptane, octane, nonane, decane, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, naphthalene or biphenyl, chlorinated hydrocarbons such as dichloroethane, trichloroethane, chlorobenzene or dichlorobenzene 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 And N- dimethyl-imidazolidinone. When carrying out the intramolecular transfer reaction without a catalyst, it is preferable to select an inert solvent having a relatively high boiling point, such as diethylene glycol, sulfolane, γ-butyrolactone, 1-methyl-2-pyrrolidone or N, N-dimethylimidazolide. Non etc. are mentioned. The obtained functional organophosphorus compound having a hydroxy group is crystalline and can be purified by recrystallization or vacuum distillation.

  Next, the industrial utility of the present invention will be described. As often described, the functional organophosphorus compound of the present invention is nonhydrolyzable and has a plurality of unsaturated groups in the molecule. Utilizing this feature, many industrially useful applications are found. The functional organophosphorus compound represented by the general formula 1 can be divided into those having no hydroxy group and those having a hydroxy group in the molecule. And these are also clearly discriminated in terms of application. One of its important uses is flame retardant PFM or flame retardant crosslinker.

  Functional organophosphorus compounds having no hydroxy group in the molecule are di- (4-allyloxyphenyl) methylphosphine oxide and the like, which are polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide, polyethylene, polypropylene, polystyrene. It is compatible with a wide range of thermoplastic resins such as AS resin, ABS resin or polyvinyl chloride resin, and functions as their PFM. That is, if these resins are added, molded, and subjected to radiation treatment, a crosslinked structure is formed in the resins, and higher heat resistance can be imparted. As the radiation, an electron beam or γ-ray is used, but at present, utilization of γ-ray by cobalt 60 has already been generalized, and since the transmission power is large, it is easier to use than the electron beam in the present invention. A feature of this application is that formation of a crosslinked structure and imparting flame retardancy can be achieved by one organophosphorus compound, and 1 to 1 functional organophosphorus compounds having no hydroxy group can be used for these resins. 25% by weight, more preferably 2 to 15% by weight, is added. Among the thermoplastic resins described above, a polyphenylene oxide resin in which a polycarbonate resin and polystyrene are mixed is particularly excellent in the flame retardant effect of the organic phosphorus compound. Addition of a compound having no hydroxy group is suitable for these resins. It is preferable to add 3 to 25% by weight, more preferably 5 to 15% by weight, of an organic phosphorus compound having no hydroxy group to these resins. If a compound having a hydroxyl group is added to a polycarbonate resin and molding is performed at a high temperature, a transesterification occurs during the molding and the mechanical strength of the polycarbonate resin is lowered. In addition, the compound having a hydroxy group is not compatible with the polyphenylene oxide resin mixed with polystyrene. In addition to the functional organophosphorus compound of the present invention, additives suitable for the respective resins can be added to these resins. Examples of additives include stabilizers, lubricants, other flame retardants, colorants such as dyes and pigments, and inorganic fillers.

  Next, an application field in which the non-hydrolyzable characteristics peculiar to the functional organophosphorus compound of the present invention can be most effectively used is a printed wiring board used in electronic equipment. A printed wiring board is mainly manufactured from an epoxy resin or a phenol resin, but many of its uses require flame retardancy.

  Among the functional organic phosphorus compounds represented by the general formula 1, those having no hydroxy group in the molecule have a plurality of unsaturated groups, and a polyepoxy compound can be obtained by epoxidation with an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide, peracid, and hypochloride. These polyepoxy compounds are maintained as non-hydrolyzable and are used as members of the epoxy resin composition. However, such an epoxidation reaction is difficult to apply to a compound having a hydroxy group in the molecule.

  Among the functional organophosphorus compounds represented by the general formula 1, those having a plurality of hydroxy groups in the molecule are suitable for use as flame retardant curing agents for epoxy resins. However, these hydroxy groups are relatively slow to react with epoxy compounds compared to other curing agents, and after pre-reaction with a sufficient excess of epoxy compound, the desired curing is further achieved. It is preferable to add an agent and finally cure. In addition, the epoxy resin used for a printed wiring board is usually reinforced with a glass fiber fabric, and these curing agents or pre-reacted substances such as methyl ethyl ketone, dimethylformamide, or N, N-dimethylacetamide are used in the production method of the board. Although it is required to be dissolved in an organic solvent, any of the epoxy resin curing agents of the present invention has sufficient solubility and can be suitably used for this purpose. In addition, the cured epoxy resin by this hardening | curing agent shows a high glass transition temperature, and this characteristic is also suitable for the use of a printed wiring board. Flame retardancy positioned at V-0 in the flame retardancy test method of UL-94 by using the curing agent of the present invention in an amount of 10 to 40% by weight, more preferably 20 to 35% by weight, based on the cured epoxy resin. Sex is obtained. In recent printed wiring boards, the miniaturization of wiring and the multi-layering have progressed remarkably, but the functional organophosphorus compound of the present invention is non-hydrolyzable, so the electrical characteristics of the board using it under severe conditions Does not deteriorate.

  Among the functional organophosphorus compounds represented by the general formula 1, those having a plurality of hydroxy groups have a plurality of unsaturated groups. The above-mentioned application as an epoxy resin curing agent is merely a curing reaction utilizing the reactivity of the hydroxy group with the epoxy group. However, by applying radiation treatment such as electron beam or γ-ray after the curing reaction, it is not possible. An epoxy resin having a high degree of cross-linking density and a high glass transition temperature due to a cross-linking reaction of saturated groups is formed. According to this cross-linking reaction, the formation of alcoholic hydroxy groups seen in the normal epoxy resin cross-linking reaction is avoided, so that a high cross-linking density and higher electrical characteristics are maintained. This technique has been newly developed by the present inventors, and can be said to be an advanced invention that is expected to have extremely high utility value in the future.

  In addition, a functional organophosphorus compound having a plurality of hydroxy groups in the molecule undergoes a condensation reaction with epichlorohydrin in the presence of alkali to obtain a polyepoxy compound, which can also be used for the same purpose as described above. I can do it.

  Epoxy resins usually consist of a combination of an epoxy compound having a plurality of epoxy groups and a curing agent reactive with the epoxy groups, and as a result of the reaction, an infusible insoluble resin is formed. . The functional organophosphorus compound according to the present invention has a function as a curing agent, and glycidyl ethers derived therefrom have a function as an epoxy compound. These are preferably used in combination with other epoxy compounds or other curing agents.

  Other epoxy compounds include bisphenol-A / epichlorohydrin condensate {2,2-bis- (4-glycidyloxyphenyl) propane}, brominated bisphenol-A / epichlorohydrin condensate, bisphenol-F / epichlorohydrin condensate (4 , 4′-diglycidyloxyphenylmethane), bisphenol-A · epichlorohydrin condensate, brominated 1,1-bis- (4-glycidyloxyphenyl) ethane, 3,3 ′, 5,5′-tetramethyl-4 , 4′-glycidyloxybiphenyl, tris- (4-glycidyloxyphenyl) methane, 1,1,2,2-tetrakis- (4-glycidyloxyphenyl) ethane, phenol novolac glycidyl ether, cresol noborac glycidyl ether, 4,4 '-(N, , N ′, N′-tetraglycidyldiaminodiphenyl) methane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, triglycidyl isocyanurate, hydrogenated bisphenol-epichlorohydrin condensate, neopentyl glycol diglycidyl ether Or a trimethylol propane triglycidyl ether etc. are mentioned. Other curing agents include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, aliphatic amines such as metaxylylenediamine or paraxylylenediamine, metaphenylenediamine, paraphenylenediamine, toluylenediamine, 4 Aromatic amines such as 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone or 1,1-bis- (4-aminophenyl) cyclohexane, polyamides, acid anhydrides, polyphenols or dicyandiamide Although very many types are known, any of them can be suitably used for the purpose of the present invention.

  A functional organophosphorus compound having a plurality of hydroxy groups in the molecule is a polyhydric phenol, and forms an intermediate between an excess amount of formaldehyde and a resol type phenol resin. When this is cured after adding 5 to 30% by weight, more preferably 10 to 25% by weight, during the production of the phenol resin composition, flame retardancy positioned at V-0 by the UL-94 test method can be obtained. This flame retardant phenolic resin is suitable for use in various electric parts and electronic equipment parts as well as printed wiring boards. Note that this phenol resin also shows no decrease in electrical insulation due to hydrolysis.

  Next, in order to further clarify the present invention, specific examples, comparative examples, and reference examples will be described. In the examples, “%” represents wt% and “parts” represents parts by weight.

(Example 1) {Synthesis of di- (41-allyloxyphenyl) methylphosphine oxide}
(Example 1-1) (Synthesis of 4-allyloxyphenyl bromide)
Into a glass 5,000 ml flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was added 1,21 g (7 mol) of 4-bromophenol and 1,000 g of 30% aqueous sodium hydroxide solution ( 7.5 mol) was added and the temperature of the contents was kept at 80 ° C. while stirring, and 551 g (7.2 mol) of allyl chloride was slowly dropped from the dropping funnel. The dropping was adjusted to a speed at which allyl chloride was gradually refluxed from the reflux condenser, and it took about 6 hours. After completion of the dropwise addition, the contents were sampled from time to time and the progress of the reaction was followed by gas chromatography (GC) analysis. Further, 4-bromophenol as a starting material almost disappeared after 4 hours. To this, 1,200 g of water and 800 g of toluene were added, and the mixture was agitated and allowed to stand, and then the lower aqueous layer was removed. Subsequently, 1,000 g of 1% aqueous sodium hydroxide solution was added, stirred for 30 minutes, allowed to stand, and then only the oil layer was collected. Toluene in the oil layer was distilled off, followed by vacuum distillation under reduced pressure of about 0.6 kilopascals to obtain about 1,400 g of 4-allyloxyphenyl bromide.

(Example 1-2) (Synthesis of 4-allyloxyphenyl magnesium bromide)
Nitrogen gas was blown into the glass five-flask having an internal volume of 3,000 ml equipped with a stirrer, a thermometer, a reflux condenser, a gas blowing port and a dropping funnel to replace the air in the flask. To this, 500 g of THF, 87.6 g (3.6 mol) of metallic magnesium and 0.1 g of iodine were charged, and nitrogen gas was slowly blown in while stirring. 200 g of a 32% THF solution of 4-allyloxyphenyl bromide was added from the dropping funnel. After 2 hours while stirring at room temperature, the flask was heated to maintain the temperature at which the contents boiled, and further 1,800 g of a 32% THF solution of 4-allyloxyphenyl bromide was added dropwise from the dropping funnel over 2 hours. . The boiling state was maintained for another hour. The temperature at this time was 65-70 degreeC. After cooling this, excess metal magnesium was removed, and a THF solution of 4-maryloxyphenyl magnesium bromide equivalent to 3 moles was obtained.

(Example 1-3) {Synthesis of di- (4-allyloxyphenyl) methylphosphine oxide}
Nitrogen gas was blown into a glass 5,000 ml flask with an internal volume of 5,000 ml equipped with a stirrer, thermometer, reflux condenser with a liquid outlet at the bottom, gas inlet and dropping funnel to replace the air in the flask. did. This was charged with 199.4 g (1.5 mol) of methyldichlorophosphine oxide (Aldrich reagent) and 1,000 g of toluene. While stirring, the temperature of the flask contents was kept at 40 ° C. From the dropping funnel, 3 mol of 4-allyloxyphenylmagnesium bromide obtained in Example 1-2, corresponding to 3 mol of THF, was added dropwise over 2 hours. After completion of dropping, the temperature in the flask was raised to 100 ° C. in 3 hours. During this time, the boiling THF was discharged from the lower part of the reflux condenser. This temperature was maintained for 2 hours, and the formation of the target product was confirmed by GC analysis. To this, 1,000 g of toluene and 500 g of 5% sulfuric acid aqueous solution were added, stirred for 30 minutes, and allowed to stand for 30 minutes. After removing the lower aqueous layer, 1,000 g of purified water was added, stirred for 30 minutes, and allowed to stand for 30 minutes. The lower aqueous layer was removed and the same operation was repeated once more. The toluene layer was transferred to a distiller having an internal volume of 3,000 ml, and toluene was distilled off. Finally, the distillation was completed at 120 ° C. at 2.6 kPascal. In the still, 490 g of a light brown viscous liquid remained, and as a result of GC analysis, it contained 96% of the main component. A part of this was taken and purified to a purity of 99% or more by the column chromatogram method, and used as analytical data for compound confirmation. The infrared absorption spectrum (IR) of the purified product is shown in FIG. 1, ³¹ PNMR is shown in FIG. 2, ¹ HNMR is shown in FIG. 3, and the results of elemental analysis show that carbon is 69.3% (theoretical value: 69.50%) and hydrogen is 6 It was 0.48% (theoretical value: 6.444%) and phosphorus was 9.42% (theoretical value: 9.433%). From these analysis results, it was confirmed that this product was di- (4-allyloxyphenyl) methylphosphine oxide. Incidentally, IR is potassium bromide tablet method, NMR is a CDC1 ₃ as a solvent, ³¹ PNMR is ¹ HNMR phosphoric acid were referenced to tetramethylsilane (TMS), respectively.

Example 2 {Synthesis of di- (3-allyl-4-hydroxyphenyl) methylphosphine oxide}
450 g of di- (4-allyloxyphenyl) methylphosphine oxide obtained in Example 1-3 and diethylene glycol were added to a 2,000 ml four-volume flask equipped with a stirrer, a thermometer, a reflux condenser and a gas inlet. 300 g was charged. While stirring the flask, nitrogen gas was slowly blown from the gas blowing port. The flask was heated to raise the temperature of the contents. In particular, after the temperature of the contents reached 160 ° C, it took 5 hours to reach 200 ° C by adjusting the heating rate. After confirming that the intramolecular transfer reaction was completed by liquid chromatography (LC) analysis, the flask was cooled to 80 ° C. To this, 800 g of isopropanol was added and slowly cooled to 0 ° C. to precipitate crystals. The crystals were filtered and washed with 400 g of cooled isopropanol. This was dried to obtain 390 g of white crystals having a purity of about 98%. The melting point of the crystal is 178.4 ° C., IR is FIG. 4, ³¹ PNMR is FIG. 5, ¹ HNMR is FIG. 6, and the results of elemental analysis are the same as those of the isomer di- (4-allyloxyphenyl) methylphosphine oxide. there were. From these results, it was confirmed that this was di- (3-allyl-4-hydroxyphenyl) methylphosphine oxide. The same NMR solvent was used as in Example 1-3, except that deuterated dimethyl sulfoxide was used.

Example 3 {Synthesis of di- (3-allyl-4-hydroxyphenyl) butylphosphine oxide}
Instead of 199.4 g of methyldichlorophosphine oxide used in Example 1-3, n-butyldichlorophosphine oxide (CAS No. 2302-80-9, manufactured by the method of the manufacturing literature extracted from Chemical abstract) 262 About 480 g of white crystals were obtained in the same manner as in Example 2 following Example 1-3, except that 0.5 g (1.5 mol) was used. The melting point of the crystal is 154 ° C., IR is FIG. 7, ³¹ PNMR is FIG. 8, ¹ HNMR is FIG. 9, and the results of elemental analysis are 70.9% for carbon (theoretical value: 71.33%) and 8.83 for hydrogen. % (Theoretical value: 8.853%) and phosphorus was 8.39% (theoretical value: 8.362%). From these analysis results, it was confirmed that this product was di- (3-allyl-4-hydroxyphenyl) butylphosphine oxide.

Example 4 {Synthesis of di- (3-allyl-4-hydroxyphenyl) phenylphosphine oxide}
Subsequent to Example 1-3, 294.5 g (1.5 mol) of phenyldichlorophosphine oxide (Aldrich reagent) was used instead of 199.4 g of methyldichlorophosphine oxide used in Example 1-3. In the same manner as in Example 2, 520 g of white crystals were obtained. The melting point of the crystal is 195 ° C., IR is FIG. 10, ³¹ PNMR is FIG. 11, ¹ HNMR is FIG. 12, and elemental analysis shows that carbon is 73.9% (theoretical value: 73.834%) and hydrogen is 5.95. % (Theoretical value: 5.938%) and phosphorus was 7.90% (theoretical value: 7.934%). From these analysis results, it was confirmed that this product was di- (3-allyl-4-hydroxyphenyl) phenylphosphine oxide.

Example 5 {Synthesis of di- (3-allyl-4-hydroxyphenyl) benzylphosphine oxide}
Example 1-3 except that 313.5 g (1.5 mol) of benzyldichlorophosphine oxide (CAS No. 1499-19-0) was used instead of 199.4 g of methyldichlorophosphine oxide used in Example 1-3. Subsequently, in the same manner as in Example 2, 530 g of white crystals were obtained. The melting point of the crystal is 195.8 ° C., the IR is FIG. 13, the ³¹ PNMR is FIG. 14, the ¹ HNMR is FIG. 15, the elemental analysis results are 74.1% carbon (theoretical value: 74.2433%), 6 hydrogen. It was 0.25% (theoretical value: 6.231%) and phosphorus was 7.70% (theoretical value: 7.685%). From these analysis results, it was confirmed that this product was di- (3-allyl-4-hydroxyphenyl) benzylphosphine oxide.

Example 6 {Synthesis of Tris- (3-allyl-4hydroxyphenyl) phosphine oxide}
Example 6-1 {Synthesis of Tris- (4-allyloxyphenyl) phosphine oxide}
Nitrogen gas was blown into a five-neck flask having an internal volume of 5,000 ml equipped with a stirrer, a thermometer, a reflux condenser having a liquid outlet at the bottom, a gas blowing port and a dropping funnel to replace the air in the flask. This was charged with 153.3 g (1.0 mol) of phosphorus oxychloride and 1,000 g of toluene. The temperature of the contents was kept at 80-110 ° C. while stirring. To this, 3 mol of THF solution of 4-allyloxyphenylmagnesium bromide obtained by the same method as in Example 1-2 was dropped from a dropping funnel in 6 hours. Meanwhile, boiling THF was discharged from the lower part of the reflux condenser and aged for another 5 hours. The formation of the target product was confirmed by GC analysis. To this, 500 g of toluene and 500 g of 5% sulfuric acid aqueous solution were added, stirred at 80 ° C. for 30 minutes, and allowed to stand for 30 minutes. After removing the lower aqueous layer, another 1,000 g of purified water was added, stirred for 30 minutes, and allowed to stand for 30 minutes. The organic layer was transferred to a distiller having an internal volume of 3,000 ml, and volatile components were removed under reduced pressure to obtain 430 g of a light brown viscous liquid. This was confirmed to be tris- (4-allyloxyphenyl) phosphine oxide by analysis such as ³¹ PNMR.

Example 6-2 {Synthesis of Tris- (3-allyl-4-hydroxyphenyl) phosphine oxide}
To a stirrer equipped with a thermometer, a reflux condenser and a gas inlet, a four-neck flask with an internal volume of 2,000 ml was charged with 420 g of tris- (4-allyloxyphenyl) phosphine oxide obtained in Example 7-1 and 500 g of diethylene glycol. Was charged. Nitrogen gas was stirred in and the flask was heated to gradually raise the temperature of the contents. After reaching 190 ° C., this temperature was maintained for 4 hours, and the completion of the intramolecular transfer reaction was known by liquid chromatography (LC) analysis. To this was added 800 g of isopropanol, and the mixture was gradually cooled to precipitate crystals. After cooling to 0 ° C., the crystals were filtered off. This was washed with 400 g of cooled isopropanol and dried. 390 g of white crystals having a melting point of 260 ° C. were obtained. This IR is shown in FIG. 16, ³¹ PNMR is shown in FIG. 17 and ¹ HNMR is shown in FIG. 18. The results of elemental analysis are as follows: carbon 72.71% (theoretical value: 72.633%), hydrogen 6.12% (theoretical value: 6 0.096%) and phosphorus 6.94% (theoretical value: 6.937%). These results confirmed that this was tris- (3-allyl-4-hydroxyphenyl) phosphine oxide.

Example 7 {Synthesis of Tris- (3-methallyl-4-hydroxyphenyl) phosphine oxide}
(Example 7-1) (Synthesis of 4-metalryloxyphenyl bromide)
In the same manner as in Example 1-1, except that 551 g (7.2 mol) of allyl chloride used in Example 1-1 was replaced with 652 g (7.2 mol) of methallyl chloride, about 4-metalryloxyphenyl bromide 1,500 g was obtained.

(Example 7-2) (Synthesis of 4-metalryloxyphenyl magnesium bromide)
The same procedure as in Example 1-2 was performed except that the 32% THF solution of 4-allyloxyphenyl bromide used in Example 1-2 was replaced with the same amount of a 34.1% THF solution of 4-metalloxyphenyl bromide. An equivalent of 3 moles of 4-metallooxyphenyl magnesium bromide in THF was obtained.

(Example 7-3) {Synthesis of Tris- (3-metallyl 4-hydroxyphenyl) phosphine oxide}
A total of 3 moles of the THF solution of 4-allyloxyphenylmagnesium bromide used in Example 6-1 was replaced with 3 moles of the 4-metallooxyphenylmagnesium bromide THF solution obtained in Example 7-2. The product obtained in the same manner as in Example 6-1 was subsequently treated in the same manner as in Example 6-2 to obtain about 400 g of white crystals having a melting point of 220 ° C. This IR is FIG. 22, ³¹ PNMR is FIG. 23, ¹ HNMR is FIG. 24, and the results of elemental analysis are as follows: carbon is 73.81% (theoretical value: 73.752%), hydrogen is 6.81% (theoretical value: 6 .808%) and phosphorus 6.35% (theoretical value: 6.340%), and these analysis results confirmed that this was tris- (3-methallyl-4-hydroxyphenyl) phosphine oxide. It was.

(Example 8)
10% of di- (4-allyloxyphenyl) methylphosphine oxide obtained in Example 1 was added to and mixed with Xylon (a mixture of polystyrene and polyphenylene oxide) manufactured by Asahi Kasei in Japan. Pellets were made on an Extruder for Model TEN-37BS testing. A test piece having a thickness of 1/8 inch conforming to the UL-94 standard was produced by an extrusion molding machine. Some of the test pieces were irradiated with γ rays from cobalt 60 for 20 seconds. The test piece of γ-ray irradiation treatment and the untreated test piece were immersed in a solder bath heated to 320 ° C. for 20 seconds. The former was almost unchanged, while the latter was significantly deformed. Thereby, the effect by γ-ray irradiation was confirmed. Moreover, in the test according to the flame retardancy test method of UL-94, the former showed the flame retardance positioned at V-0.

(Comparative Example 1)
A test piece having a thickness of 1/8 inch conforming to the UL-94 standard was prepared by using the Xylon used in Example 8 as it was with an extrusion molding machine. A portion of this was irradiated with gamma rays from cobalt 60 for 20 seconds. The test piece of γ-ray irradiation treatment and the untreated test piece were immersed in a solder bath heated to 320 ° C. for 10 seconds, but both were similarly deformed, and the effect of the γ-ray irradiation treatment was not observed. Moreover, in the test according to the flame retardancy test method of UL-94, both showed the flame retardance positioned as V-2. From this result and the result of Example 8, it was demonstrated that di- (4-allyloxyphenyl) methylphosphine oxide has a function as a PFM and a function as a flame retardant with respect to Xylon.

Example 9
Di- (3-allyl-4-hydroxyphenyl) methyl obtained in Example 2 was added to 100 parts of an epoxy resin mainly composed of 2,2-bis- (4-glycidyloxyphenyl) propane manufactured by Kokuto Chemical, Korea. 40 parts of phosphine oxide was added, mixed well, and reacted at 100 ° C. for 5 hours to obtain a preliminary reaction product. In the same manner, 45 parts of di- (3-allyl-4-hydroxyphenyl) butylphosphine oxide obtained in Example 3 was replaced with 45 parts of di- (3-allyl-4-hydroxyphenyl) obtained in Example 4. ) 48 parts of phenylphosphoxide and 49 parts of di- (3-allyl-4-hydroxyphenyl) benzylphosphoxide obtained in Example 5 were added to obtain 4 types of pre-reacted materials. . Each of these pre-reacted materials was mixed with 17 parts of 4,4′-diaminodiphenylmethane and allowed to cure at 110 ° C. for 3 hours, and then 1/8 inch thick 4 meeting UL-94 flammability test specifications. Types of test specimens were cut out. In the flame test of the test piece, it shows flame retardancy positioned at V-0. From these results, it was proved that all of the functional organophosphorus compounds obtained in Examples 2 to 5 had both a function as a curing agent for epoxy resin and a function as a flame retardant.

(Example 10)
Tris- (3-allyl-4-hydroxyphenyl) phosphine oxide obtained in Example 6 on 100 parts of an epoxy resin mainly composed of 2,2-bis- (4-glycidyloxyphenyl) propane manufactured by Kokuto Chemical, Korea 45 parts were added to 100 parts of epoxy resin and 49 parts of tris- (3-methallyl-4hydroxyphenyl) phosphine oxide obtained in Example 7 were added and mixed, and a preliminary reaction was performed at 100 ° C. for 5 hours. After adding 33 parts of bisphenol-A to each of these and causing a curing reaction at 110 ° C. for 3 hours, two kinds of test pieces having a thickness of 1/8 inch conforming to the UL-94 combustion test standard were cut out. In the flame test of the test piece, the flame retardancy positioned at V-0 was shown. From these results, it was proved that all of the functional organophosphorus compounds obtained in Examples 6 and 7 had both a function as a curing agent for epoxy resin and a function as a flame retardant.

(Example 11)
Six types of test pieces prepared in Example 9 and Example 10 were irradiated with γ rays from cobalt 60 for 20 seconds. As for the glass transition temperature measured by the thermal analysis method, the specimen obtained in Example g was found to increase by about 20 ° C. by irradiation with γ rays. In addition, the test piece obtained in Example 10 was found to increase by about 15 ° C. by γ-ray irradiation.

(Reference Example 1)
In order to demonstrate the non-hydrolyzability of the functional organophosphorus compound of the present invention, the following experiment was conducted. For comparison with the functional organophosphorus compounds obtained in Examples 1 to 7 in 100 g of 30% potassium hydroxide in methanol, commercially available triphenyl phosphate (triphenyl phosphate) and commercially available triallyl phosphate (phosphorus) 10 g each of triallyl acid) was added and heated for 24 hours in the boiling state of methanol. When the change was examined by LC analysis, no change was found in the functional organophosphorus compound of the present invention. Triphenyl phosphate was diphenyl phosphate and phenol, and triallyl phosphate was diallyl phosphate and allyl. It was completely hydrolyzed with alcohol. However, what can be salted with potassium hydroxide is considered to form a salt, but LC analysis could not distinguish it.

It is an infrared absorption spectrum of the compound obtained in Example 1-3. It is a ³¹ PNMR figure of the compound obtained in Example 1-3. ¹ is a ¹ HNMR diagram of a compound obtained in Example 1-3. FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 2. 3 is a ³¹ PNMR diagram of the compound obtained in Example 2. FIG. ¹ is a ¹ HNMR diagram of a compound obtained in Example 2. FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 3. 3 is a ³¹ PNMR diagram of the compound obtained in Example 3. FIG. ¹ is a ¹ HNMR diagram of a compound obtained in Example 3. FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 4. 4 is a ³¹ PNMR diagram of the compound obtained in Example 4. FIG. ¹ is a ¹ HNMR diagram of a compound obtained in Example 4. FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 5. 3 is a ³¹ PNMR diagram of the compound obtained in Example 5. FIG. ¹ is a ¹ HNMR diagram of a compound obtained in Example 5. FIG. It is an infrared absorption spectrum of the compound obtained in Example 6-2. It is a ³¹ PNMR figure of the compound obtained in Example 6-2. ¹ is a ¹ HNMR diagram of a compound obtained in Example 6-2. It is an infrared absorption spectrum of the compound obtained in Example 7-3. It is a ³¹ PNMR figure of the compound obtained in Example 7-3. ¹ is a ¹ HNMR diagram of a compound obtained in Example 7-3. FIG.

Claims (15)

A functional organophosphorus compound represented by the general formula 1 and having a plurality of unsaturated groups in the molecule.

(In Formula 1, R ¹ and R ² represent a 4-allyloxyphenyl group, a 3-allyl-4-hydroxyphenyl group, or a 3-methallyl-4-hydroxyphenyl group, and R ³ represents 1 to 7 carbon atoms. It represents a hydrocarbon group, 3-allyl-4-hydroxyphenyl group or 3-methallyl-4-hydroxyphenyl group.) A functional organophosphorus compound, wherein R ¹ and R ^{2 in} formula 1 are 4-allyloxyphenyl groups and R ³ is a methyl group. {Di- (4-allyloxyphenyl) methylphosphine oxide} A functional organophosphorus compound wherein R ¹ and R ^{2 in} formula 1 are 3-allyl-4-hydroxyphenyl groups and R ³ is a methyl group. {Di- (3-allyl-4-hydroxyphenyl) methylphosphine oxide} A functional organophosphorus compound wherein R ¹ and R ^{2 in} formula 1 are 3-allyl-4-hydroxyphenyl groups and R ³ is a butyl group. {Di- (3-allyl-4-hydroxyphenyl) butylphosphine oxide} A functional organophosphorus compound in which R ¹ and R ^{2 in} formula 1 are 3-allyl-4-hydroxyphenyl groups and R ³ is a phenyl group. {Di- (3-allyl-4-hydroxyphenyl) phenylphosphine oxide} A functional organophosphorus compound wherein R ¹ and R ^{2 in} formula 1 are 3-allyl-4-hydroxyphenyl groups and R ³ is a benzyl group. {Di- (3-allyl-4-hydroxyphenyl) benzylphosphine oxide} A functional organophosphorus compound in which R ¹ , R ² and R ^{3 in} formula 1 are all 3-allyl-4-hydroxyphenyl groups. {Tris- (3-allyl-4-hydroxyphenyl) phosphine oxide} A functional organophosphorus compound in which R ¹ , R ² and R ^{3 in} formula 1 are all 3-methallyl-4-hydroxyphenyl groups. {Tris- (3-methallyl-4-hydroxyphenyl) phosphine oxide} A feature is that an organophosphorus compound represented by the general formula 2 and a substituted magnesium halide represented by the general formula 3 are subjected to a condensation reaction, followed by an oxidation reaction or (and) an intramolecular transfer reaction if necessary. A process for producing a functional organophosphorus compound according to claim 2.

(In formula 2, R ⁴ represents a hydrocarbon group having 1 to 7 carbon atoms, and n represents 0 or 1)

(In Formula 3, R ⁵ represents a 4-allyloxyphenyl group or a 4-metalryloxyphenyl group, and X represents a chlorine atom or a bromine atom.)   The condensed magnesium halide represented by the general formula 3 is condensed with phosphorus trichloride, triphenyl phosphite, or phosphorus oxychloride, and further oxidized if necessary, followed by intramolecular transfer reaction. A process for producing a functional organophosphorus compound according to claim 7 or 8.   A flame-retardant, heat-resistant, characterized by subjecting a polystyrene-polyphenylene oxide resin molded product containing 3 to 25% by weight of the functional organophosphorus compound according to claim 2 to radiation treatment such as electron beam or γ-ray. Manufacturing method for functional resin molded products.   A flame retardant epoxy resin composition comprising the functional organophosphorus compound according to claim 3.   A flame retardant epoxy resin composition comprising 10 to 40% by weight of the functional organophosphorus compound according to claim 3 to 8.   A high glass transition characterized by subjecting a flame retardant epoxy resin composition containing the functional organophosphorus compound according to claim 3 to 8 to heat curing and then irradiation with radiation such as an electron beam or γ-ray. Manufacturing method of epoxy resin with temperature. 9. A flame retardant epoxy resin composition containing 10 to 40% by weight of the functional organophosphorus compound according to claim 3 to 8 is heat-cured and then subjected to radiation treatment such as electron beam or gamma ray. A method for producing an epoxy resin having a high glass transition temperature.

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