KR20100058933A - Cyclic organo phosphorus compound and preparation method thereof - Google Patents

Abstract

PURPOSE: A cyclic organo phosphorus compound is provided to ensure flame retardant and to manufacture various derivatives using responsive site. CONSTITUTION: A cyclic organo phosphorus compound has a structure of chemical formula 1. In chemical formula 1, R1-R5 are dependently hydrogen, halogen, substituted or unsubstituted C1-C18 alkyl, C1-C18 alkoxy, C4-C20 cycloalkyl, C4-C20 heteroaryl, C6-C20 aryl, or C6-C20 aryloxy; m IS 1-4 integer; n is 1 or 2; and x is 0 or 1. A method for preparing the cyclic organo phosphorus compound of chemical formula 1 comprises: a step of condensing 1,1':4',1''-tephenyl-2',5'-diol with trichloride to obtain a compound 1a; a step of hydrolyzing the compound 1a to obtain a compound 1b; and a step of cyclodehydrating the compound 1b to obtain a compound 1-1.

Description

Cyclic organophosphorus compound and its manufacturing method {CYCLIC ORGANO PHOSPHORUS COMPOUND AND PREPARATION METHOD THEREOF}

The present invention relates to a cyclic organophosphorus compound, and more particularly, to a cyclic organophosphorus compound useful as a stabilizer, a flame retardant or a raw material thereof for organic polymer materials, and a method for preparing the same.

Organophosphorus compounds are industrially used as plasticizers, stabilizers or flame retardants of polymeric materials, and toxic substances are widely used as pesticides and insecticides. Recently, the use of an organophosphorus compound as a flame retardant attracts attention.

As a combustible polymer material among conventional flame retardants, an organic halogen compound has been used a lot from a high flame retardant effect and an economic viewpoint. In particular, the use of an antimony flame retardant such as antimony trioxide together with the bromine flame retardant has a feature that the flame retardancy is further improved. However, in the event of fire, toxic gases such as HBr may be used to cause asphyxia, as well as to be toxic upon incineration, and to generate dioxine, a carcinogen, and also to develop antimony flame retardants used with bromine flame retardants. Due to sex, its use is increasingly regulated, starting with Europe.

Accordingly, in recent years, research on non-halogen flame retardants has been actively conducted, and various eco-friendly flame retardants have been developed. Examples of non-halogen flame retardants include phosphorus-based, nitrogen-based compounds, silicon-based, boron-based flame retardants, or metal oxides or metal hydroxide flame retardants. Of these, organophosphorus compounds are considered as flame retardants that can replace halogen-based flame retardants, and mainly include phosphates or phosphonates and monomolecular or condensation.

Triphenyl phosphate (TPP) is known as the simplest compound among phosphates. It has a problem of volatilization when forming a polymer material at high temperature due to its small molecular weight, and a problem of weakening the softening point of the resin and weakening the mechanical strength by acting as a plasticizer of the polymer material. There is this. In addition, secondary contamination may occur as the flame retardant is eluted from the resin. In order to solve this problem, Japanese Patent Laid-Open No. 59-202240 and Japanese Patent Laid-Open No. 2-18336 disclose condensed phosphorus flame retardants containing two phosphorus elements in a molecule using hydroquinone, resorcinol, bisphenol derivatives, etc. Doing. However, the condensed organophosphorus flame retardant also exhibits significantly lower characteristics than the halogen-based flame retardant in terms of heat resistance, hydrolysis resistance, and flame retardancy. In addition, when the phosphate ester type TPP or condensation type flame retardant is added to the ester type polymer resin (PET, PC, etc.), the resin physical property decreases due to the transesterification reaction. In order to improve the heat resistance of these organophosphorus flame retardants, the molecular weight should be increased or the molecular structure should be solid. In order to have hydrolysis resistance and transesterification resistance, the phosphonate type, phosphinate type, or phosphine oxide type molecules may be used. It is desirable to design it. In addition, to increase the flame retardancy, it is necessary to increase the phosphorus content in the molecule.

In contrast, Japanese Patent Application Laid-Open No. 60-126293 (U.S. Patent No. 4,618,693), which is a special cyclic organophosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and their Derivatives are disclosed. DOPO is useful as a stabilizer, flame retardant, or raw material for the manufacture of flame retardants in organic polymer materials. Among the organophosphorus compounds derived therefrom, it has good hydrolysis resistance and transesterification resistance and is widely used in flame retardant fields requiring high properties. It is used. This compound is obtained by condensation reaction of o-phenylphenol (2-hydroxybiphenyl) and phosphorus trichloride, followed by hydrolysis, and is used as a stabilizer or flame retardant of polymer materials. Moreover, various derivatives are synthesize | combined from these and are used as a flame retardant of a polymeric material. These publications include Japanese Patent Laid-Open Publication Nos. 53-13479, 10-130287, 11-106619, 11-130287, 2000-336204, 2001-115047, 2001-115047, etc. It is described in detail in.

However, although the cyclic organophosphorus compounds are useful as stabilizers, flame retardants or raw materials for their preparation of organic polymer materials, the flame retardancy needs to be further improved, and the compound has only one functional group (PH group). As a result, it is difficult to create various derivatives from these so as to be applied to a wide range of applications of high molecular compounds.

Accordingly, it is an object of the present invention to provide a novel organophosphorous compound and a method for preparing the same, which are useful as an additive such as a flame retardant or stabilizer of organic polymer materials, can be induced into various kinds of organophosphorus compounds, and have high flame retardancy and strength. It is.

In order to achieve the above object, the present invention provides a cyclic organophosphorus compound represented by the following formula (1):

Where

R ₁ to R ₅ are each independently hydrogen or halogen, substituted or unsubstituted, C _1-18 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _4-20 heteroaryl, C _{6- 20} aryl or C _6-20 aryloxy;

m is an integer from 1 to 4; n is 1 or 2; x is 0 or 1.

The cyclic organophosphorus compound hydrolyzes a compound obtained by condensation of 1,1 ': 4', 1 ''-terphenyl-2 ', 5'-diol with phosphorus trichloride in the presence of a catalyst, It may be prepared by dehydration cyclization. In addition, various derivatives may be prepared by conducting a condensation reaction, an addition reaction, or a substitution reaction with a compound having one or more groups of R ₁ to R ₅ defined in Chemical Formula 1.

The cyclic organophosphorus compound of the present invention has a high phosphorus content, has excellent flame retardancy, excellent strength, and has two reactive sites in the molecule, so that the cyclic organophosphorus compound can be directly introduced into the polymer main chain and can be prepared in various derivatives. It can be used as a flame retardant or stabilizer in polymer materials.

Hereinafter, the present invention will be described in more detail.

In Formula 1, R ₁ to R ₅ are each independently unsubstituted C _1-18 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _4-20 heteroaryl, C _6-20 aryl Or C _6-20 aryloxy; Or each independently, halogen, amino, thio, cyano, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, silyl, boranyl, C _1-18 alkyl, C _1-18 alkoxy, C C _1-18 alkyl, substituted with one or more groups selected from the group consisting of _4-20 cycloalkyl, C _4-20 heteroaryl, C _6-20 aryl, C _6-20 aryloxy and C _7-20 aralkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _4-20 heteroaryl, C _6-20 aryl or C _6-20 aryloxy.

In addition, as the substituted or unsubstituted C _1-18 alkyl group capable of the substituents R ₁ to R ₅ in Formula 1, specifically methyl, ethyl, propyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2 -Carboxyethyl, 2-carboxypropyl, 2-alkoxycarbonylethyl, 2- (2-hydroxyethoxy) carbonylethyl, 2-alkoxycarbonylpropyl, 2- (2-hydroxyethoxy) propyl, 2 -Cyanoethyl, 2-cyanopropyl, 2-carbamoylethyl, 2-carbamoylpropyl, 2,3-dicarboxypropyl, glycidyl, benzyl, 4-methylbenzyl and the like are preferred; Specific examples of the substituted or unsubstituted C _1-18 alkoxy group are methoxy, ethoxy, isopropoxy, t-butoxy and the like. Further, as the substituted or unsubstituted C _6-20 aryl group, specifically, phenyl, naphthyl, 4-methylphenyl, 2-methylphenyl, 2,5-dimethylphenyl 2,5-dihydroxyphenyl, 1,4-dihydrate Hydroxy-2-naphthyl and the like are preferred; The substituted or unsubstituted Specific examples of the C _6-20 aryloxy group include phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 4-t-butylphenoxy, 2 -t-butylphenoxy, 2,4-di-t-butylphenoxy, 4-hydroxyphenoxy, 3-hydroxyphenoxy and the like are preferable.

An example of such a method for preparing a compound of the present invention is shown in Scheme 1 below. In Scheme 1, 1,1 ': 4', 1 ''-terphenyl-2 ', 5'-diol and phosphorus trichloride are condensed in the presence of a catalyst to obtain the following compound 1a, which is hydrolyzed to obtain After obtaining compound 1b, the following compound 1-1 can be synthesize | combined by dehydration cyclization.

In Scheme 1, Compound 1-1 is the simplest compound in which x = 1 and R ₁ to R ₅ are all hydrogen in the compound of the present invention according to Chemical Formula 1, and may be used as a precursor for synthesizing other compounds.

In addition, Compound 1a and Compound 1b, which are reaction intermediates in Scheme 1, can be used by themselves as additives or reactive intermediates such as flame retardants. However, for compound 1a Since P-Cl is a strong active group, it is preferable to prepare various derivatives therefrom rather than adding it to a polymer material by itself.

From compound 1a, stable organophosphorus compounds represented by the following formula (2) which can be added to the polymer material by using simple chemical techniques such as condensation reaction or substitution reaction are derived. They have trivalent phosphorus atoms and are suitable for use as stabilizers for various polymeric materials:

In Chemical Formula 2,

R ₁ and R ₂ are the same as defined in Formula 1

Preferably, each independently is substituted or unsubstituted C _1-18 alkyl, C _1-18 alkoxy, C _6-20 aryloxy or hydrogen.

The compound of Formula 2 is compound 1a is formed by the Friedel-Craft condensation reaction of 1,1 ': 4', 1 ''-terphenyl-2 ', 5'-diol with phosphorus trichloride. The final compound of formula 2 can be obtained through condensation reaction under a base catalyst such as tertiary amine. For example, the compound of Formula 2 wherein R ₁ and R ₂ are substituted with methoxy, ethoxy, isopropoxy, phenoxy, etc. may be prepared by reacting compound 1a with methanol, ethanol, isopropanol, phenol and the like. At this time, it is preferable to use triethylamine as the base catalyst.

In addition, the compound 1-1 of the present invention can be used as a stabilizer or a flame retardant with respect to a polymer material by itself, from which it is possible to derive an organophosphorus compound represented by the following formula (3) using a simple synthetic means, It has a wide range of applications as flame retardants or stabilizers and has the advantage of being applied to various kinds of polymer materials:

In Chemical Formula 3,

R ₁ and R ₂ are the same as defined in Formula 1,

Preferably, each independently is a substituted or unsubstituted C _1-18 alkyl group, C _6-20 aryl or hydrogen,

Especially in hydrogen, methyl, ethyl, propyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-carboxyethyl, 2-carboxypropyl, 2-alkoxycarbonylethyl, 2- (2-hydroxy Methoxy) carbonylethyl, 2-alkoxycarbonylpropyl, 2- (2-hydroxyethoxy) propyl, 2-cyanoethyl, 2-cyanopropyl, 2-carbamoylethyl, 2-carbamoylpropyl , 2,3-dicarboxypropyl, glycidyl, benzyl, 4-methylbenzyl, 2,5-dihydroxyphenyl, 1,4-dihydroxy-2-naphthyl, or compound 1-1 and epoxy compound Residues of adducts of the family And so on.

Such a method for preparing the compound of Formula 3, in particular, when R ₁ or R ₂ of Formula 3 is substituted or unsubstituted C _1-18 alkyl or C _6-20 aryl, especially glycidyl, benzyl or 4 In the case of -methylbenzyl, it can manufacture by condensation reaction of the corresponding halogen compound and compound 1-1, and it is preferable at this time that a base exists.

In addition, R ₁ or R ₂ in Formula 3 is methyl, ethyl, propyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-carboxyethyl, 2-carboxypropyl, 2-alkoxycarbonylethyl , 2- (2-hydroxyethoxy) carbonylethyl, 2-alkoxycarbonylpropyl, 2- (2-hydroxyethoxy) propyl, 2-cyanoethyl, 2-cyanopropyl, 2-carba Moylethyl, 2-carbamoylpropyl, 2,3-dicarboxypropyl, 2,5-dihydroxyphenyl, 1,4-dihydroxy-2-naphthyl, or compound 1-1 with an epoxy compound In the case of residues of adducts, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, formaldehyde, acetoaldehyde, ethylene oxide, acrylic acid, methacrylic acid, acrylic esters, hydroxyethyl Acrylates, methacrylic acid esters, hydroxyethyl methacrylates, acrylonitrile, It can be prepared by addition reaction of methacrylonitrile, acrylamide, methacrylamide, itaconic acid, parabenzoquinone, 1,4-naphthoquinone, or an epoxy compound with compound 1-1. At this time, it is preferable that a trace amount of metal ions or organic bases are present, and as the epoxy compound, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, methyl hydroquinone, 2,5-di-t-butylhydroquinone and reso Lysine, methylresorcin, 4,4'-dihydroxydiphenylether, dihydroxynaphthalin, 4,4'-biphenol or 3,3 ', 5,5'-tetramethyl-4,4'- Diglycidyl esters of dihydric phenols such as biphenols can be used.

Since the cyclic organophosphorus compound of the present invention is excellent in heat resistance and water resistance, high phosphorus content, and excellent in flame retardancy, it is possible to solve problems such as various problems due to the heat resistance, hydrolyzability and transesterification of the phosphate ester system as flame retardants, or flame retardancy. It can be solved, has high strength, and has two reactive sites in the molecule, so that it is possible to manufacture an additive flame retardant in a form suitable for the characteristics of the resin and can be directly introduced into the polymer main chain. It can be used in various flame retardants and stabilizers of polymer resins for electronic materials.

Specifically, as the organic polymer material which can use the cyclic organophosphorus compound of the present invention as a flame retardant or other additives, polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene Butadiene copolymer, acrylonitrile butadiene copolymer, styrene acrylonitrile copolymer, ABS resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene tere Phthalates, polyethylene dinaphthoates, terephthalic acid, 1,4-butanediol, polybutylene ether copolymers, elastomers, polycarbonates, polyamides, polyimides, polyurethanes, epoxy resins, phenolic resins, melamine resins, urea resins, liquid crystalline A high molecular compound, a cellulose acetate, etc. are mentioned.

In order to make this invention clearer, although a specific Example is given and described below, the manufacturing method of this invention is not limited only to a following example.

Preparation of Cyclic Organo Phosphorus Compounds

Example 1 (See Scheme 1 above)

Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 17, p. 2998-3007] to synthesize 1,1 ': 4', 1 ''-terphenyl-2 ', 5'-diol. A 5 L volume flask equipped with a dropping funnel is installed in a reflux cooler connected to the upper portion of the gas treatment device, and the 1,1 ': 4', 1 ''-terphenyl-2 ', 5'-diol 786.9 g (3.0 mol) and 1 L of o-dichlorobenzene were added and dissolved.

Thereafter, 892.7 g (6.5 mol) of phosphorus trichloride was added dropwise over about 1 hour using a dropping funnel at room temperature, and then the temperature of the reaction solution was gradually raised over about 3 hours to 140 ° C. At this time, hydrogen chloride gas began to be released at a temperature of about 50 ° C., and the reaction was terminated when generation of hydrogen chloride gas was minimal when additional reaction was performed for about 2 hours after reaching the temperature of 140 ° C. After the temperature was lowered to room temperature again, 8.18 g (0.06 mol) of zinc chloride was added, and the temperature was gradually raised to 170 ° C. and reacted for about 6 hours. After the completion of the reaction, nitrogen gas was slowly blown to recover the unreacted phosphorus trichloride, thereby obtaining a resultant compound having compound 1a and o-dichlorobenzene as main components and having moisture sensitive properties.

500 mL of o-dichlorobenzene was further added to the resultant, and distilled water was added using a dropping funnel for about 1 hour with vigorous stirring. The reaction mixture was then heated to 90 ° C. for 3 hours, cooled, and filtered to crystallize white crystals. The solid was filtered with 1 L of water / ethanol (1: 1, v / v) mixed solvent. Washed and dried in vacuo at about 50 ° C. to give 682 g of a white powdery compound 1b.

100 g of the obtained compound 1b was dispersed in 500 mL of toluene, placed in a 1 L flask equipped with a Dean-Stark trap device connected to a thermometer, a gas inlet, and a cooling capacitor, and heated to a breaking point. It was refluxed. The azeotropic reflux of the toluene and the resulting water removed the separated water through the bottom of the Dean-Stark trap. The reaction proceeded for 24 hours, after which the reaction was terminated when no more water appeared in the Dean-Stark trap, followed by hot filtration to remove small amounts of insolubles in the reactants. Subsequently, the reaction was cooled to room temperature, the solvent was removed under reduced pressure, washed with methanol, and 86 g of a dark yellow powder was obtained through vacuum drying.

Elemental analysis of the result showed that the result was Compound 1-1, as analyzed by phosphorus 17.5% (theoretical value: 17.49%), hydrogen 3.42% (theoretical value: 3.41%), and carbon 60.2% (theoretical value: 61.03%). .

Example 2 (see Scheme 2 below)

In a 2 L round bottom flask equipped with a reflux condenser, 35.4 g (0.1 mol) of Compound 1-1 obtained in Example 1 was dissolved in 900 mL of dichloromethane. 9.3 g (BTMA, 0.05 mol) of benzyltrimethylammonium chloride, 29.0 g (0.21 mol) of anhydrous potassium carbonate, and 35.9 g (0.21 mol) of benzylbromide were added and refluxed for 48 hours with stirring. After filtering the reaction, the solvent of the filtrate was removed and then recrystallized from toluene to obtain 38.5 g of the compound 1-2 shown in the following scheme. As a result of elemental analysis, it was confirmed that the resultant product was compound 1-2 as analyzed by phosphorus 11.6% (theoretical value: 11.59%), hydrogen 4.48% (theory value: 4.53%), and carbon 71.8% (theory value: 71.91%). It became.

Example 3 (see Scheme 3 below)

To a 1 L round bottom flask equipped with a reflux cooler and a dropping funnel, 35.4 g (0.1 mol) of compound 1-1 obtained in Example 1, 0.5 mL of concentrated hydrochloric acid, and 400 mL of ethanol were added and refluxed. After about 1 hour, 0.1 mL of concentrated hydrochloric acid was added and 59.3 g of triethyl orthoformate was added dropwise over about 4 hours. When triethyl orthoformate was added dropwise, concentrated hydrochloric acid was added in 0.1 mL increments every 30 minutes. After dropping was completed, the reaction was terminated after refluxing for 1 hour. The solvent and unreacted reactant were then removed via distillation under reduced pressure and dried in vacuo to afford 33.8 g of the following compound 1-3 as a yellow powder.

Example 4 (see Scheme 3 below)

20.6 g (0.05 mol) of compound 1-3 and 0.4 g (2 mmol) of ethyl-p-toluenesulfonate were added to a 250 mL round bottom flask, and the temperature was heated to 180 ° C. After 12 hours, when the displacement reaction was completed, the temperature was lowered to room temperature and washed three times with 150 mL of distilled water to obtain 20 g of the final compound 1-4. Elemental analysis of the result showed that the resultant product was found to be Compound 1-4, as analyzed by phosphorus 15.0% (theoretical value: 15.10%), hydrogen 4.88% (theoretical value: 4.91%), and carbon 64.3% (theoretical value: 64.39%). It became.

Comparative Example 1

In order to compare with the cyclic organophosphorus compound of this invention, triphenyl phosphate (Aldrich) was prepared as a conventional flame retardant.

Test Example

Example In order to evaluate the flame retardancy of the cyclic phosphorus-based flame retardant prepared in Comparative Example was prepared as follows. Commercially available KD-213 (Kukdo Chemical, Bisphenol-A, EEW 730-840) was used as the solid epoxy resin used for the specimen preparation, and dicyanodiamine (DICY) was used as the curing agent.

First, each compound obtained in the above Examples and Comparative Examples in 100 parts by weight of the epoxy resin 20 parts by weight, and 10 parts by weight of DICY were mixed while heating at a temperature, and then pulverized with a mortar and pestle to prepare a specimen in which the epoxy resin, the curing agent, and the flame retardant were evenly mixed. The powder prepared on a Teflon plate with a frame of 3 mm in height was applied to a thickness of 3 mm and the curing reaction was carried out in an oven maintained at 200 ° C. for 1 hour, and then the temperature was lowered to room temperature to 12.7 mm in width and 127 mm in length. Was prepared.

The specimens thus prepared were evaluated for flame retardancy using the UL-94 V test method established by the US Underwriters Laboratories. In addition, for the prepared specimen, the strength was measured by the KS M 3015 method, a tensile strength test method. The results are summarized in Table 1 below.

As shown in Table 1, it can be seen that the cyclic organophosphorus compound according to the embodiment of the present invention not only has excellent flame retardancy, but also excellent properties such as strength compared to the conventional organophosphorus compound according to the comparative example. . In the above, the present invention has been described with reference to the above embodiments, which are only examples, and various modifications and other equivalent embodiments apparent to those of ordinary skill in the art will be claimed. It should be understood that this can be done within the scope.

Claims (14)

A cyclic organophosphorus compound having the structure of Formula 1 [Formula 1]

Where R ₁ to R ₅ are each independently hydrogen or halogen, substituted or unsubstituted, C _1-18 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _4-20 heteroaryl, C _{6- 20} aryl or C _6-20 aryloxy; m is an integer from 1 to 4; n is 1 or 2; x is 0 or 1. The method of claim 1, R ₁ to R ₅ are each independently, Halogen, amino, thio, cyano, hydroxy, carbonyl, carboxy, carbamoyl, epoxy, phosphoryl, silyl, boranyl, C _1-18 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl Substituted with one or more groups selected from the group consisting of C _4-20 heteroaryl, C _6-20 aryl, C _6-20 aryloxy and C _7-20 aralkyl, C _1-18 alkyl, C _1-18 alkoxy, C _4-20 cycloalkyl, C _4-20 heteroaryl, C _6-20 aryl or C _6-20 aryloxy. The method of claim 1, The substituted or unsubstituted C _1-18 alkyl group is methyl, ethyl, propyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-carboxyethyl, 2-carboxypropyl, 2-alkoxycarbonyl Ethyl, 2- (2-hydroxyethoxy) carbonylethyl, 2-alkoxycarbonylpropyl, 2- (2-hydroxyethoxy) propyl, 2-cyanoethyl, 2-cyanopropyl, 2-car Cyclic organophosphorus compound, characterized in that barmoylethyl, 2-carbamoylpropyl, 2,3-dicarboxypropyl, glycidyl, benzyl, or 4-methylbenzyl. The method of claim 1, The substituted or unsubstituted C _1-18 alkoxy group is methoxy, ethoxy, isopropoxy, or t-butoxy, cyclic organophosphorus compound. The method of claim 1, The substituted or unsubstituted C _6-20 aryl group is phenyl, naphthyl, 4-methylphenyl, 2-methylphenyl, 2,5-dimenylphenyl 2,5-dihydroxyphenyl, or 1,4-dihydroxy It is 2-naphthyl, The cyclic organophosphorus compound. The method of claim 1, The above substituted or unsubstituted C _6-20 The aryloxy group is phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,4-dimethylphenoxy, 2,6-dimethylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy , 2,4-di-t-butylphenoxy, 4-hydroxyphenoxy, or 3-hydroxyphenoxy, Cyclic organophosphorus compound. The method of claim 1, R ₁ and R ₂ are each independently, substituted or unsubstituted, C _1-18 alkyl, C _1-18 alkoxy, C _6-20 aryl or C _6-20 aryloxy or hydrogen; The R ₃ to R ₅ are all hydrogen, cyclic organophosphorus compound. The method of claim 1, R ₁ and R ₂ are each independently hydrogen, methyl, ethyl, propyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-carboxyethyl, 2-carboxypropyl, 2-alkoxycarbonyl Ethyl, 2- (2-hydroxyethoxy) carbonylethyl, 2-alkoxycarbonylpropyl, 2- (2-hydroxyethoxy) propyl, 2-cyanoethyl, 2-cyanopropyl, 2-car Barmoylethyl, 2-carbamoylpropyl, 2,3-dicarboxypropyl, glycidyl, benzyl, 4-methylbenzyl, 2,5-dihydroxyphenyl, or 1,4-dihydroxy-2- Naphthyl; R ₃ to R ₅ are all hydrogen; Said x = 1, Cyclic organophosphorus compound. The method of claim 1, A cyclic organophosphorus compound, characterized in that any one of the following compounds:

,

,

, And

. The method of claim 1, A cyclic organophosphorus compound, which is used as a flame retardant or stabilizer of an organic polymer material. a) condensation of 1,1 ′: 4 ′, 1 ″ -terphenyl-2 ′, 5′-diol with phosphorus trichloride in the presence of a catalyst to prepare Compound 1a; b) hydrolyzing the compound 1a to prepare the following compound 1b; And c) sequentially dehydrating the compound 1b to prepare the following compound 1-1; Optionally, d) condensation, addition or substitution of compound 1-1 with a compound having at least one group of R ₁ to R ₅ as defined in claim 1, wherein the cyclic organophosphorus compound of claim 1 Manufacturing method of:

The method of claim 11, Step d), the compound 1-1, Condensation with a corresponding halogen compound of glycidyl, benzyl or 4-methylbenzyl;  Trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, formaldehyde, acetoaldehyde, ethylene oxide, acrylic acid, methacrylic acid, acrylic acid esters, hydroxyethyl acrylate, methacrylic acid esters, Characterized by addition reaction with hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, itaconic acid, parabenzoquinone, 1,4-naphthoquinone, or an epoxy compound, Method for producing cyclic organophosphorus compound. a) condensation of 1,1 ′: 4 ′, 1 ″ -terphenyl-2 ′, 5′-diol with phosphorus trichloride in the presence of a catalyst to prepare Compound 1a; And b) below, including the R ₁ and R ₂ comprising at least one compound and the condensation reaction or substitution reaction with a group of the definitions of compound 1a in claim 1, method for producing a cyclic organic phosphorus compound of the general formula (2):

[Formula 2]

Wherein R ₁ and R ₂ are the same as defined in Chemical Formula 1. The method of claim 13, Step b) is characterized in that the compound 1a condensation reaction with methanol, ethanol, isopropanol or phenol, Method for producing cyclic organophosphorus compound.