KR20130039568A - Cyclic organo nitrogen-phosphorus compounds and flame retardant resin having the same and preparation method thereof - Google Patents

Abstract

PURPOSE: A cyclic organic nitrogen-phosphorus compound is provided to ensure high flame retardancy and to be used as an additive of a flame retardant or a stabilizing agent without strength reduction of a polymer material when mixing in the polymer material. CONSTITUTION: A cyclic organic nitrogen-phosphorus compound is denoted by chemical formula 1, 2, 3, or 4. A method for preparing the cyclic organic nitrogen-phosphorus compound of chemical formula 1 comprises a step of reacting phosphorous pentachloride and 1,8-diamino naphthalene under the presence of a catalyst. A method for preparing the cyclic organic nitrogen-phosphorus compound of chemical formula 2 comprises a step of reacting o-phenylene diamine with phosphorous pentachloride under the presence of a catalyst. A method for preparing the cyclic organic nitrogen-phosphorus compound of chemical formula 3 comprises a step of reacting 2-aminobenzonitrile with phosphorous pentachloride under the presence of a catalyst. A method for preparing the cyclic organic nitrogen-phosphorus compound of chemical formula 4 comprises a step of reacting o-phenylene diamine with alkyl phosphorous bichloride under the presence of a catalyst. The flame retardant resin contains the cyclic organic nitrogen-phosphorus compound and organic polymer resin.

Description

Cyclic organic nitrogen-phosphorus compound, preparation method thereof, and flame-retardant resin containing same TECHNICAL FIELD

The present invention relates to a cyclic organic nitrogen-phosphorus compound, a flame retardant resin containing the same, and a method for preparing the same, more particularly, a cyclic organic nitrogen-phosphorus compound useful as a stabilizer, a flame retardant, or a raw material thereof. It relates to a flame-retardant resin and a method for producing the same comprising the same.

In recent years, interest in the protection of the global environment, the protection of the living environment, and the like has increased, and non-halogen-based compounds containing no halogen are used as flame retardants, and from the viewpoint of environmental protection, harmful gases such as halogens and residues at the time of combustion. There is also a growing demand for flame retardants that do not occur.

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

Typical ways in which a flame retardant may exhibit a flame retardant effect are, for example, as follows. First, as a solid phase inhibition, in this way the flame retardant forms char to prevent heat from being transferred inside. Next is vapor phase inhibition, which changes the chemical structure and stops the radical chain reaction to prevent combustion. Third, there is a heat operation method, in which water (H ₂ O) is generated during combustion to cool the surface.

The organophosphorus flame retardant compound is an additive and mainly exhibits a flame retardant effect by thermal action.It mainly produces polymethic acid by pyrolysis when combusted, and it is used for dehydration when it forms a protective layer and when polymethic acid is produced. It is known that the carbon film produced thereby exhibits a flame retardant effect in a manner that blocks oxygen to prevent combustion.

Organic nitrogen-phosphorus flame retardant is widely used as an additive type, and is known as an intumescent flame retardant to provide flame retardancy by controlling the combustion by thermal decomposition of char generated by thermal action of nitrogen gas.

Among the conventional flame retardants, an organic halogen compound has been widely used in view of high flame retardant effect and economical efficiency. In particular, the use of an antimony flame retardant such as antimony trioxide together with a bromine flame retardant is characterized by further improved flame retardancy. However, in the event of fire, toxic gases such as HBr may be used to cause asphyxia, as well as to be toxic when incinerated, and may generate dioxine, a carcinogen. 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.

Among them, organophosphorus compounds are considered as flame retardants that can replace halogen-based flame retardants, and mainly include phosphates, phosphonates or phosphazenes, and monomolecular or condensed compounds.

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 low molecular weight. 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. Hei 2-18336 disclose a condensed phosphorus flame retardant containing two phosphorus elements in a molecule using hydroquinone, resorcinol, bisphenol derivatives, etc. It is. 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 the organophosphorus flame retardant, the molecular weight should be increased or the molecular structure should be firm. In order to have hydrolysis resistance and ester exchange resistance, phosphonate type, phosphinate type, phosphine oxide type or phospha It is desirable to design molecules in genotypes. In addition, to increase the flame retardancy, it is necessary to increase the phosphorus content in the molecule.

In this regard, 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 these The derivative of is disclosed and has been studied a lot as a gas phase functional phosphorus flame retardant useful in epoxy materials, but the flame retardancy is not sufficient due to the small number of gas phase functional radicals.

Japanese Patent Laid-Open No. 1985-126293 JP-A-1984-202240 Japanese Patent Laid-Open No. 1990-18336

Accordingly, an object of the present invention is high flame retardancy, does not lower the strength of the polymer material when mixed with the polymer material, is useful as an additive such as a flame retardant or stabilizer of organic polymer material, and can be used as a derivative of various kinds An organic nitrogen-phosphorus compound, a flame retardant resin containing the same, and a method for producing the same are provided.

In order to achieve the above object, the present invention provides a cyclic organic nitrogen-phosphorus compound represented by the following formula (1), (2), (3) or (4).

[Formula 1]

[Formula 2]

(3)

[Formula 4]

Where

R ₁ to R ₃ are each independently, hydrogen, halogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,

Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.

The present invention provides a method for preparing a cyclic organic nitrogen-phosphorous compound of Formula 1, comprising the step of cyclizing a 1,8-diamino naphthalene and phosphorus pentachloride in the presence of a catalyst. It provides a manufacturing method.

In addition, the present invention is a method for producing a cyclic organic nitrogen-phosphorous compound of Formula 2, the cyclic organic nitrogen-compound prepared by the step of cyclizing the o-phenylenediamine and phosphorus pentachloride in the presence of a catalyst It provides a manufacturing method.

In addition, the present invention is a method for producing a cyclic organic nitrogen-phosphorous compound of Formula 3, a cyclic organic nitrogen-phosphorus prepared by the step of cyclizing 2-aminobenzonitrile and phosphorus pentachloride in the presence of a catalyst Provided are methods for preparing the compounds.

In addition, the present invention is a method for preparing a cyclic organic nitrogen-phosphorous compound of Formula 4, a cyclic organic nitrogen-phosphorus compound prepared by the step of cyclizing the o-phenylenediamine and phosphorus dichloride in the presence of a catalyst It provides a method of manufacturing.

In addition, the present invention provides a flame-retardant resin comprising a cyclic free nitrogen-phosphorous compound of any one of Formulas (1) to (4).

The organic phosphorus-nitrogen compound according to the present invention is environmentally friendly because it does not contain a halogen element, and is excellent in heat resistance and water resistance, and contains phosphorus and nitrogen at the same time, so it is excellent in flame retardancy and stability, and phosphorus (P) in the molecule Since it has two reactive sites in the element, not only can be directly introduced into the polymer main chain, but also various derivatives can be prepared and used as a flame retardant or stabilizer in polymer materials in various fields.

1 is a graph showing the results of GC-mass measurement for Compound 1.
2 is a graph showing the DSC measurement results for the compound 1.
3 is a graph showing the GC-mass measurement results for the compound 2.
4 is a graph showing the DSC measurement results for the compound 2.
5 is a graph showing the GC-mass measurement results for the compound 3.
6 is a graph showing the DSC measurement results for the compound 3.

In order to achieve the above object, the present invention provides a cyclic organic nitrogen-phosphorus compound represented by the following formula (1), (2), (3) or (4).

[Formula 1]

[Formula 2]

(3)

[Formula 4]

Where

R ₁ to R ₃ are each independently a halogen, hydrogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,

Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.

In addition, the present invention includes the above formula 1 to formula 4 production method, it will be described in detail below.

As a method for preparing the cyclic organic nitrogen-phosphorus compound of Chemical Formulas 1 and 2 of the present invention, 1,8-diaminonaphthalene or o-phenylenediamine and phosphorus pentachloride are cyclized in the presence of a catalyst to give intermediate compound 1-1. Or compound 2-1. In this case, the catalyst may be an inorganic base or an organic base. Examples of the inorganic base include sodium hydroxide and potassium hydroxide. Examples of the organic base include amine-based pyridine, triethylamine, DBU, and the like, but triethylamine is preferable.

Scheme 1

Scheme 2

The intermediate compound 1-1 or compound 2-1 obtained above may be subjected to a substitution reaction using an organometallic salt to prepare an organic nitrogen-phosphorus compound having a phosphorus-carbon bond to obtain a target compound of Formula 1 or Formula 2, The present invention also provides a production method for producing them.

At this time, the organometallic salts include substituted or unsubstituted alkyl and phenyl metal salts represented by R ₁ to R ₂ , and examples of the metal include sodium, potassium, and lithium elements, and lithium alkyl or phenyllithium is preferable. Do.

In addition, the present invention also includes a compound represented by the following formulas (5) to (10) obtained by reacting intermediate compound (1-1) or compound (2-1) with a metal alkoxy salt, metal alkylthio salt, alkyl amine, etc. .

The preparation method of the cyclic organic nitrogen-phosphorus compound of Chemical Formula 3 of the present invention is as follows. 2-Aminobenzonitrile and phosphorus pentachloride are cyclized in the presence of a catalyst to obtain intermediate compound 3-1. The intermediate compound 3-1 obtained above may be subjected to a substitution reaction using an organometallic salt to produce an organic nitrogen-phosphorus compound having a phosphorus-carbon bond, thereby obtaining a target product, and the present invention also provides a production method for producing these compounds. do.

Scheme 3

At this time, the organometallic salt in [Scheme 3] includes substituted or unsubstituted alkyl and phenyl metal salts represented by R ₁ to R ₂ , and examples of the metal include sodium, potassium and lithium elements, and lithium alkyl or phenyl. Lithium and the like are preferable to use.

In addition, the present invention also includes a compound represented by the following Chemical Formulas 11 to 13 obtained by reacting Intermediate Compound 3-1 with a metal alkoxy salt, metal alkylthio salt, alkyl amine, etc. in Scheme 3.

The preparation method of the cyclic organic nitrogen-phosphorus compound of Chemical Formula 4 of the present invention is as follows. Provided is a process for preparing a compound of formula (4) obtained by cyclization of o-phenylenediamine and alkyl phosphorus dichloride in the presence of a catalyst.

[Reaction Scheme 4]

In addition, the present invention also includes the compounds of the following formula (14) to formula (16) obtained when R is alkoxy or metal alkylthio, alkyl amine in Scheme 4.

In addition, since the organic nitrogen-phosphorous compound according to the present invention is used by mixing with a thermoplastic resin in order to be used as an additive flame retardant, it is preferable to melt similarly to the melting temperature of the thermoplastic resin, so that a differential scanning calorimeter (DSC) Melting point 145? It is preferable that it is -220 degrees. Compounds of the present invention are useful as additive flame retardants due to their high melting point

In another aspect, the present invention provides a flame-retardant resin containing the compound of Formula 1 to Formula 16.

In another aspect, the present invention provides a flame-retardant resin containing the formula 1 to formula 16 cyclic free nitrogen-phosphorus compound, the flame retardant resin can impart flame retardancy to various organic polymer materials. Examples of the organic polymer material include polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, Styrene acrylonitrile copolymer, acrylonitrile butadiene styrene (ABS) resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene tere Phthalate, polyethylene dynaphthoate, terephthalic acid-1,4-butanediol polybutylene ether copolymer elastomer, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, liquid crystal Although a polymeric polymer, cellulose acetate, etc. are mentioned, It is not limited to these.

Mixing method of the organic nitrogen-phosphorus compound and the organic polymer material according to the present invention is not particularly limited, roll mill, super mixer, Henschel mixer, high speed mixer, ball mill, steel mill, sand mill, progress mill, homo mixer The mixing device may be mixed using a homogenizer, a jet mill, a batch mixer, a twin screw extruder, a single screw extruder, and the like may be used alone or in combination of two or more.

When the organic nitrogen-phosphorus compound of the present invention is used as a flame retardant resin, the content thereof varies greatly depending on the type of the organic polymer material to be blended and the target flame retardant performance. To 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight. If it is included in less than 1 part by weight, the effect of improving the flame retardancy is not sufficient, and if it exceeds 50 parts by weight, it is not preferable because of the change in physical properties of the resin according to the addition amount.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.

Example  1 to 2 and Comparative example  1: Preparation of Organic Nitrogen-Phosphorus Compound

Synthetic example  1. Preparation of naphthalene type organic nitrogen-phosphorus compound (Compound 1)

Synthesis of Compound 1-1

1,8-diamino naphthalene (50 g), triethylamine (64 g), and solvent THF (800 ml) were put into a round bottom flask (2L), and it stirred for 4 hours in argon atmosphere. PCl ₅ (49 g) was slowly added dropwise to the flask, followed by stirring while maintaining 35 ° C to 45 ° C for 24 hours. At this time, the insolubles during the reaction were filtered out using silica gel. After that, the filtrate was dried to obtain a dark yellow powder. Thereafter, the mixture was washed with n-hexane, followed by filtration to obtain Compound 1-1 as a pale yellow intermediate (76 g).

Synthesis of Compound 1

Bromobenzene (60 g) was dissolved in THF (600 ml) in a round bottom flask (1 L) and then cooled to -78 ° C. After adding BuLi (191 ml) and stirring at the same temperature for 2 hours, Compound 1-1 (30 g) dissolved in THF was slowly added dropwise. After the dropwise addition, the mixture was stirred at -78 ° C for 3 hours, and then stirred at room temperature for 8 hours. After completion of the reaction, the solvent was removed, THF, and the solid product was dissolved in toluene, and a hot filter was filtered in a filtration apparatus coated with silica to remove salts insoluble in toluene. The filtered solvent is removed with a rotary evaporator and washed several times with n-hexane. The light brown powder product Compound 1 was purified by passing through a silica column to obtain Compound 1 as a gray powder (11 g). 1 and 2 show the results of GC-mass and DSC measurements for Compound 1. The melting point was 182 ^° C as a result of DSC measurement.

Synthetic example  2. Benzene type  Preparation of Organic Nitrogen-Phosphorus Compound (Compound 2)

Synthesis of Compound 2-1

O-phenylenediamine (50 g), triethylamine (94 g) and solvent THF (800 ml) were added to a round bottom flask (2 L), and the mixture was stirred for 4 hours under an argon atmosphere. PCl ₅ (96g) was slowly added dropwise to the flask, followed by stirring while maintaining 35 ° C to 45 ° C for 24 hours. At this time, the insolubles during the reaction were filtered out using silica gel. After that, the filtrate was dried to obtain a dark yellow powder. Thereafter, the mixture was washed with n-hexane, followed by filtration to obtain Compound 2-1 as a pale yellow intermediate (58 g).

Synthesis of Compound 2

Bromobenzene (46 g) was dissolved in THF (500 ml) in a round bottom flask (1 L) and then cooled to -78 ° C. After adding BuLi (125 ml) and stirring at the same temperature for 2 hours, Compound 2-1 (50 g) dissolved in THF was slowly added dropwise. After the dropwise addition, the mixture was stirred at -78 ° C for 3 hours, and then stirred at room temperature for 8 hours. After completion of the reaction, the solvent was removed, THF, and the solid product was dissolved in toluene, and a hot filter was filtered in a filtration apparatus coated with silica to remove salts insoluble in toluene. The filtered solvent was removed with a rotary evaporator and washed several times with n-hexane. The light brown powder product Compound 2 was purified by passing through a silica column to obtain Compound 2 as a gray powder (18 g). 3 and 4 show the results of GC-mass and DSC measurements for Compound 3. As a result of DSC measurement, the melting point was 229 ° C.

Synthetic example  3. Benzene type  Preparation of Organic Nitrogen-Phosphorus Compound (Compound 3)

Synthesis of Compound 3-1

2-aminobenzonitrile and PCl ₅ (88 g) were dissolved in PhCl (881 g) in a round bottom flask (2 L). After slowly increasing the temperature of the reactor to 110 ℃ and maintained for 3 hours, the reaction was terminated by checking the reaction by TLC. After cooling to room temperature to precipitate a pale yellow solid product. The resulting solid product was washed several times with n-hexane and separated by silica column to give compound 3-1 as a light yellow intermediate (32 g).

Synthesis of Compound 3

Bromobenzene (48 g) was dissolved in THF (500 ml) in a round bottom flask (1 L) and then cooled to -78 ° C. After adding BuLi (191 ml) and stirring at the same temperature for 2 hours, Compound 3-1 (30 g) dissolved in THF was slowly added dropwise to the flask. After dropping, the mixture was stirred at -78 ° C for 3 hours, and then stirred at room temperature for 8 hours. After the reaction, the solvent is removed, the solid product is dissolved in toluene, and silica hot filter is performed to remove the salt. The filtered solvent is removed with a rotary evaporator and washed several times with n-hexane. The light brown powder product was obtained (10 g) as light gray powder 3 through a silica column. 5 and 6 show the results of GC-mass and DSC measurements for Compound 3. As a result of DSC measurement, the melting point was 161 占 폚.

Synthetic example  4: Benzene type  Preparation of Organic Nitrogen-Phosphorus Compound (Compound 4)

In a round bottom flask (1 L) o-phenylenediamine (25 g) and Et3N (47 g) were dissolved in THF (250 ml) followed by the substitution of 1-propylphosphonic dichloride (45 g). After completion of the reaction, the solvent was removed and extracted with ethyl acetate. After drying the organic layer, a yellow powder product was obtained through pale silica column to obtain compound 4 (27 g) as a light yellow powder. The melting point was 144 ^° C as a result of DSC measurement.

Experimental Example  1: Physical property evaluation

Gas Chromatography-Mass Spectrometer (GC-MS; JMS-600W, manufactured by JEOL) and Differential Scanning Calorimeter (DSC) for the compounds prepared according to Synthesis Examples 1 to 3 ; DSC 823e, manufactured by METTLER TOLEDO) was used for mass spectrometry and thermal properties. 1 and 2 show the results of Synthesis Example 1, FIG. 3 and FIG. 4 show the results of Synthesis Example 2, and FIGS. 5 and 6 show the results of Synthesis Example 3, respectively.

1 and 2, it was confirmed that the compound prepared in Synthesis Example 1 is the target compound of the formula (1), the molecular weight is 340, and the melting point is 182 ℃. 3 and 4 it was confirmed that the compound prepared in Synthesis Example 2 is the target compound of the chemical chamber 2, the molecular weight is 290, the melting point was 229 ℃. 5 and 6 it was confirmed that the compound prepared in Synthesis Example 3 is the target compound of the chemical chamber 3, the molecular weight is 378, and the melting point is 161 ℃.

Experimental Example  2: flame retardancy evaluation

In order to evaluate the flame retardancy of the compound according to the present invention, a specimen was prepared by the following method, and the flame retardancy was evaluated using the UL-94V test method set by the US Underwriters Laboratories.

First, 10 parts by weight of each of the compounds prepared in Synthesis Example 1 were added to 100 parts by weight of HISF (high-impact polystyrene) resin of BASF Corporation, and added to a twin screw extruder to be pushed in a temperature range of 230 to 280 ° C. for flame retardancy. A resin was prepared, and the prepared flame retardant resin was dried at 80 ° C. for 3 hours, and then molded under an injection molding machine under conditions of a molding temperature of 200 to 280 ° C. and a mold temperature of 50 to 70 ° C. to prepare a specimen for evaluation of flame retardancy. .

In addition, except that the compound prepared in Synthesis Example 3 instead of Synthesis Example 1 was prepared in the same manner as in Example 2, instead of the compound of Synthesis Example 1 to compare with the cyclic organic nitrogen-phosphorus compound of the present invention A specimen was prepared in the same manner as in Comparative Example 1 except that triphenyl phosphate (Aldrich Co., Ltd.), which was a conventional flame retardant, was used. At this time, the specimens were manufactured in 5 X 0.5 X 1/1 (inches) size, and five specimens were prepared for each sample.

When evaluating the flame retardancy of the manufactured specimens, the test standard was adjusted to 20 mm in accordance with IEC 60695-11-10 using small flames (50 W). It was positioned mm apart. Time t1 to install the specimen and light it with a burner for 10 seconds, then remove the burner and turn off the fire on the specimen, t1, time to remove the burner after the fire for 10 seconds, and then turn off the light on the specimen, t2, fire The time t3 until the glow disappeared and the flame retardance was evaluated according to the following criteria. The results are shown in Table 1 below.

<Flame Retardation Evaluation Criteria>

V-0: t1 and t2 of each of the specimens are less than 10 seconds each, t1 + t2 of the five specimens is less than 50 seconds, and t2 + t3 of each of the specimens is less than 30 seconds, and no flaming occurs due to sparking. Occation

V-1: t1 and t2 of each of the specimens are less than 30 seconds each, t1 + t2 of the five specimens is less than 250 seconds, and t2 + t3 of each of the specimens is less than 60 seconds, and no flaming occurs due to sparks. Occation

V-2: When t1 and t2 of each of the specimens are less than 30 seconds each, t1 + t2 of the five specimens is less than 250 seconds, and t2 + t3 of each of the specimens is less than 60 seconds, and burning occurs due to sparking.

Experimental Example  3: strength evaluation

In order to evaluate the strength of the compound according to the present invention, the same specimens as those of Examples 1, 2 and Comparative Example 1 prepared in the flame retardancy evaluation were used, and the specimen size used in the strength evaluation was the same as that of the UL test specimen. The size was fabricated and the flexural strength was compared.

In order to measure the flexural strength, the specimen was placed on two points separated by 25 mm, and the stress and distortion were measured by applying a load in a vertical direction in which the specimen was placed at a constant speed until the fracture of the specimen occurred. The measurement was performed using a 3 point bending test method using Tinius Olsen's UTM (Universal Testing Machine, Instrument Model: H100Ks) to measure the stiffness of the specimen when the specimen was loaded at a constant speed of 20 mm per minute. Elongation was 50N. The results are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Flammability V-1 V-1 V-2 Strength (N / mm2) 27.5 31.7 17.3

As shown in Table 1, in the case of Example 1, t1 was measured at 18 seconds, and thus flame retardancy was evaluated as V-1. In addition, in Example 2, t1 was 20 seconds and the flame retardancy was V-1. In addition, in Examples 1 to 2, the cotton was not ignited by fire. On the contrary, in the case of Comparative Example 1, t1 was measured for 28 seconds, and ignition due to sparking occurred, resulting in flame retardancy of V-2.

In addition, as shown in Table 1, Example 1 and Example 2 has a high strength of 27.5 and 31.7 N / mm2, respectively, while Comparative Example 1 has a relatively low strength of 17.3 N / mm2 there was.

From the above experimental results, it can be seen that the organic nitrogen-phosphorus compounds according to the present invention of Examples 1 and 2 have superior flame retardancy compared to the flame retardants of the conventional organophosphorus compounds according to the comparative example. In addition, it was found that the strength of the specimen mixed with the flame retardant resin of the present invention was superior to that of the specimen mixed with the flame retardant resin of 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 noted that this can be done within the scope.

Claims (8)

The cyclic organic nitrogen-phosphorus compound represented by the following formula (1), (2), (3) or (4).
[Formula 1]

(2)

(3)

[Chemical Formula 4]

In this formula,
R ₁ to R ₃ are each independently, hydrogen, halogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,
Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl. A method for preparing a cyclic organic nitrogen-phosphorous compound of formula (I) comprising the step of cyclizing 1,8-diamino naphthalene and phosphorus pentachloride in the presence of a catalyst.
[Formula 1]

In this formula,
R ₁ to R ₂ are each independently, hydrogen, halogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,
Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.
A method for preparing a cyclic organic nitrogen-phosphorous compound represented by the following Chemical Formula 2, comprising the step of cyclizing the o-phenylenediamine and phosphorus pentachloride in the presence of a catalyst.
(2)

In this formula,
R ₁ to R ₂ are each independently, hydrogen, halogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,
Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.
A method for preparing a cyclic organic nitrogen-phosphorus compound represented by the following Chemical Formula 3, comprising the step of cyclizing 2-aminobenzonitrile and phosphorus pentachloride in the presence of a catalyst.
(3)

In this formula,
R ₁ to R ₃ are each independently, hydrogen, halogen, substituted or unsubstituted with substituents substituted with a C _{1 -18} alkyl, substituents unsubstituted or substituted with a C _{1 -18} alkyl, substituents unsubstituted unsubstituted C _{4- 20} cycloalkyl, substituted with a substituent or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl,
Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.
A method for preparing a cyclic organic nitrogen-phosphorous compound represented by the following Chemical Formula 4, comprising the step of cyclizing the o-phenylenediamine and the alkyl phosphorus dichloride in the presence of a catalyst.
[Chemical Formula 4]

In this formula,
R ₁ is substituted with hydrogen, halogen, optionally substituted with a substituent or unsubstituted C _{1 -18} alkyl, substituted with a substituent or unsubstituted C _{1 -18} alkyl, substituted with a substituent or unsubstituted C _{4 -20} cycloalkyl, an optionally substituted or unsubstituted C _{4 -20} heteroaryl, substituted with a substituent or unsubstituted C _{6 -20} aryl, and
Wherein the substituents are each optionally halogen, amino, thio, phosphoryl, phosphine sulfinyl, carbonyl, silyl, borane yl, C _{1 -18} alkyl, C _{1 -18} alkoxy, C _{4 -20} cycloalkyl, C _{4 -20} heteroaryl, a group C _{6 -20} aryl, which is one or more C _{6 -20} aryloxy or selected from the group consisting of C _{7 -20} aralkyl.
A flame retardant resin comprising the cyclic free nitrogen-phosphorus compound of claim 1 and an organic polymer resin.
The method of claim 6, wherein the organic polymer resin is polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene-butadiene copolymer, acrylonitrile-butadiene Ene copolymer, styrene acrylonitrile copolymer, acrylonitrile butadiene styrene (ABS) resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, Polybutylene terephthalate, polyethylene dynaphthoate, terephthalic acid-1,4-butanediol polybutylene ether copolymer elastomer, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, It is selected from the group consisting of urea resin, liquid crystalline high molecular compound, cellulose acetate Flame retardant resin, characterized in that. The flame-retardant resin according to claim 6, wherein the cyclic free nitrogen-phosphorous compound is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the organic polymer material.

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