KR101143387B1 - Organic Phosphorous-nitrogen compound having oxazolinone derivatives, preparation method thereof and flame retardant composition containing the same - Google Patents

Abstract

The present invention relates to an organic phosphorus-nitrogen-based compound comprising oxazolinone useful as a flame retardant of an organic polymer material, a method for preparing the same, and a flame-retardant composition comprising the same, wherein the organic phosphorus-nitrogen-based compound according to the present invention is heat-resistant and water-resistant. And since it is excellent in flame retardancy, it can be usefully used for the use of a flame retardant of a thermoplastic polymer, especially a polymer resin for electric and electronic materials.

Description

Organic Phosphorous-nitrogen compound having oxazolinone derivatives, preparation method about and flame retardant composition containing the same}

The present invention relates to an organophosphorus-nitrogen compound containing an oxazolinone derivative, a method for preparing the same, and a flame retardant composition comprising the same.

As flame retardants for conventional flammable polymer materials, halogen-based flame retardants have been frequently used in view of high flame retardant effects and economics. In particular, in the general-purpose thermoplastic resin, which is difficult to secure flame retardancy, an antimony flame retardant such as antimony trioxide is used as a flame retardant or auxiliary agent together with a bromine flame retardant to improve flame retardancy. However, bromine-based flame retardants not only cause suffocation by generating toxic gases such as HBr during fire, but also generate dioxin, a strong carcinogen during incineration. Because of its carcinogenicity, its use is regulated.

Accordingly, in recent years, non-halogen-based eco-friendly flame retardants have been required. 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, phosphorus compounds are considered to be the most active flame retardants to replace halogen flame retardants, and monomolecular or condensed phosphates or phosphonates are used. Triphenyl phosphate (TPP) is known as the most basic compound among phosphates, but TPP has a problem of being easily volatilized during the molding process of a polymer material which is carried out at a high temperature. There is a problem of weakening the physical properties, and also, since the flame retardant is easily eluted from the resin, there is a problem of reducing flame retardancy and secondary pollution.

In order to solve this problem, Japanese Patent Laid-Open No. 59-202240 and Japanese Patent Laid-Open No. Hei 2-18336 use hydroquinone, resorcinol, bisphenol derivatives and the like to condense phosphorus-based flame retardants containing two phosphorus elements in a molecule. The use of is being started. However, such condensed phosphorus-based flame retardant has a problem that the flame retardancy is not only degraded with time, but also the effect is significantly lower than the conventional halogen-based flame retardant in terms of heat resistance, hydrolysis resistance and flame retardancy. In addition, when the phosphate ester type TPP or condensed phosphorus flame retardant is added to an ester type polymer resin (PET, PC, etc.), there is a problem in that the resin physical properties are lowered due to a transesterification reaction.

In order to solve problems such as heat resistance, it is necessary to increase the molecular weight of the flame retardant or to strengthen the molecular structure, and to have hydrolysis resistance and ester exchange resistance, a hydrophobic group or a hindered substituent is introduced, or It is desirable to design molecules in a direction that reduces the number of bonds and promotes phosphorus-carbon bonds or phosphorus-nitrogen bonds.

It is known that the flame retardant compound may have a phosphorus-nitrogen covalent bond in a molecule to increase the stability and flame retardancy of the flame retardant. Such flame retardants include ammonium polyphosphate and melamine phosphate, but most of these nitrogen-containing phosphorus compounds have low water resistance, and in particular, melamine phosphate requires additional flame retardant additives due to low flame retardancy, thereby inferior mechanical properties of raw materials. There are disadvantages to falling. In addition to the phosphate of ethylene diamine is used, but this also has a problem of low water resistance and heat resistance.

Thus, the present inventors can solve problems such as heat resistance, hydrolysis and transesterification of the conventional phosphate ester, and while studying to develop a phosphorus compound having excellent heat resistance, water resistance, and flame retardancy, an oxazolinone derivative is included. Phosphorus-nitrogen-based compound is prepared, and the compound is excellent in heat resistance and water resistance, excellent flame retardancy due to carbon dioxide generation due to decomposition of phosphorus-nitrogen bond and oxazolinone, and it is possible to manufacture flame retardant in a form suitable for the characteristics of resin. The present invention has been found to be useful as a flame retardant of polymers, particularly polymer resins for electrical and electronic materials.

An object of the present invention is to provide an organophosphorus-nitrogen compound containing an oxazolinone derivative.

Another object of the present invention is to provide a method for preparing an organophosphorus-nitrogen compound including the oxazolinone derivative.

Still another object of the present invention is to provide a flame retardant composition comprising an organic phosphorus-nitrogen-based compound including the oxazolinone derivative.

In order to achieve the above object, the present invention provides an organic phosphorus-nitrogen-based compound containing an oxazolinone derivative represented by the following formula (1).

[Formula 1]

(In Formula 1, R ¹ , R ² , Oz, X, Y ¹ , Y ² , L, m, n, y and l are as described herein.)

The present invention also provides a method for preparing an organophosphorus-nitrogen compound including the oxazolinone derivative.

Furthermore, the present invention provides a flame retardant composition comprising an organic phosphorus-nitrogen-based compound including the oxazolinone derivative.

The organic phosphorus-nitrogen-based compound including the oxazolinone derivative according to the present invention has excellent heat resistance and water resistance, and has excellent flame retardancy due to oxygen blocking effect due to carbon dioxide generation due to phosphorus-nitrogen bond and decomposition of oxazolinone, and The flame retardant can be manufactured in a form suitable for properties, and thus it can be usefully used as a flame retardant of general purpose polymers, especially polymer resins for electric and electronic materials.

1 is a GC-Mass spectrum of an organic phosphorus-nitrogen-based compound including an oxazolinone derivative according to an embodiment of the present invention.
2 is a DSC graph of an organophosphorus-nitrogen-based compound including an oxazolinone derivative according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a compound having a phosphorus-nitrogen bond containing an oxazolinone derivative represented by the following Chemical Formula 1.

In Chemical Formula 1,

R ¹ and R ² are hydrogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C ₁ to C ₁₀ straight or branched chain alkyl, C ₂ to C ₁₀ straight chain Or branched alkenyl, C ₂ to C ₁₀ straight or branched alkynyl, C ₁ to C ₁₀ alkoxy, C ₃ to C ₁₀ cycloalkyl, C ₆ To C ₁₀ aryl, 5 to 10 membered heteroaryl, or C ₆ to C ₁₀ aryloxy group or C ₇ to C ₁₀ arylalkyl, wherein R ¹ and R ² are unsubstituted or substituted with the substituents described above. Can be substituted;

Oz is an oxazolinone derivative substituent selected from the group consisting of the following substituents,

Wherein R ³ to R ⁸ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group;

L is nitrogen, oxygen, sulfur, phosphorus or carbonyl, silyl, boranyl, C ₁ to C ₁₀ straight or branched chain alkyl, C ₂ to C ₁₀ straight or branched alkenyl, C ₂ to C ₁₀ straight chain Or a side chain alkynyl, C ₁ to C ₁₀ alkoxy, C ₃ to C ₁₀ cycloalkyl, C ₆ to C ₁₀ aryl, 5 to 10 membered heteroaryl, or C ₆ to C ₁₀ aryloxy group , Wherein L may be unsubstituted or substituted with all substituents defined in R ¹ and R ² ;

X is oxygen, sulfur or selenium;

Y ¹ is R 1 or Oz;

Y ² is R ¹ , R ² or Oz;

l is 1 or 2;

m is 1 or 2;

n is an integer from 0 to 10;

y is 0 or 1;

l is 1 when n and y are 0,

If y is 1 then Y ¹ is Oz and l is m.

Preferably, the phosphorus-nitrogen flame retardant compound of Chemical Formula 1 is selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

(3)

[Formula 4]

(In Chemical Formulas 2 to 4,

R ¹ , R ² , X, Y, L, Oz are the same as defined in Formula 1,

a is an integer of 1 to 3,

b is an integer of 1 to 2.)

More preferably, L is selected from the group consisting of the following substituents.

Specific examples of the compound represented by Formula 1 of the present invention are as follows:

(1) 3,3 ', 3' '-phosphoryltribenzo [d] oxazol-2 (3H) -one;

(2) phenyl bis (2-oxobenzo [d] oxazol-3 (2H) -yl) phosphinate;

(3) 3,3 '-(phenylphosphoryl) dibenzo [d] oxazol-2 (3H) -one;

(4) 3,3 '-(phenylphosphoryl) dioxazolidin-2-one;

(5) 1,3-phenylene bis (bis (2-oxooxazolidin-3-yl) phosphinate;

(6) 1,3-phenylene bis (methyl (2-oxooxazolidin-3-yl) phosphinate);

(7) bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) 2-oxooxazolidin-3-ylphosphonate;

(8) bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) phenyl phosphate;

(9) 1,3-phenylene bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) bis (2-oxooxazolidin-3-ylphosphonate); And

(10) 1,3-phenylene bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) diphenyl diphosphate.

The structural formulas of the compounds according to the present invention are shown in Table 1 below.

Chemical formula constitutional formula Melting point


1a

244-245 ℃

1b

118 ℃

1c

152 ℃
1d

105 ℃
1e

101 ℃
1f

88 ℃

1 g

137 ℃

1h

171 ℃

1i

132 ℃

1j

127 ℃

In addition, the present invention is a phosphorus-nitrogen containing an oxazolinone derivative of Formula 1 by reacting an oxazolinone derivative (Oz-H) and a reactive compound containing phosphorus of Formula 5 in a solvent, as shown in Scheme 1 below It provides a method for producing a system compound.

Scheme 1

(In Scheme 1,

R ¹ , R ² , Oz, X, Y ¹ , Y ² , L, m, n, y and l are the same as defined in Chemical Formula 1,

Z is a halogen or hydroxy group

Z ¹ is Z or R ^1. )

In the production method according to the present invention, the oxazolinone derivative Oz-H compound may be used 2-oxazolinone (2-oxazolinone), 2-benzoxazolinone (2-Benzoxazolinone).

In the preparation method according to the present invention, the compound containing the phosphorus of Formula 5 is phenyl dichlorophosphate, phenyl phosphate, phenyl phosphonic dichloride, phenyl phosphonic dichloride, phenyl dichloro phosphate, phosphorus oxychloride, phenyl Lene diphosphorodichlorate, phenylene bis (methylphosphonochlorate), chlorophosphorylbis (oxy) bis (3,1-phenylene) diphosphorodichlorate, phenoxyphosphorylbis It is preferable that (oxy) bis (3,1-phenylene) diphosphorodichlorate or the like is used.

In Scheme 1, the Oz-H compound is preferably used in an amount of 1 to 5 equivalents based on 1 equivalent of the reactive compound containing phosphorus of Chemical Formula 5.

In the production method according to the invention, the solvent may be used any one selected from the group consisting of chloroform, tetrahydrofuran, dimethylformamide, distilled water or a mixed solvent thereof.

In addition, it is preferable to further use tertiary amines, such as triethylamine, and bases, such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydroxide, at the time of the said reaction from a viewpoint of reaction yield improvement and reaction time shortening. At this time, the base is preferably used in 1 to 10 moles per 1 equivalent of the compound of Formula 2.

The reaction is preferably carried out at room temperature to 150 ℃ for 2 to 48 hours.

In addition, the present invention provides a flame retardant composition containing an organic phosphorus-nitrogen-based compound including the oxazolinone derivative of the formula (1).

The organic phosphorus-nitrogen-based compound including the oxazolinone derivative according to the present invention has excellent heat resistance and water resistance, and has excellent flame retardancy due to carbon dioxide generation due to phosphorus-nitrogen bond and decomposition of oxazolinone, and is suitable for the characteristics of the resin. It is possible to manufacture a flame retardant can be usefully used as a flame retardant of a general-purpose polymer, especially polymer resin for electrical and electronic materials.

The flame retardant composition may be prepared by mixing a compound of Formula 1 and a polymer resin.

 The polymer resin is 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 terephthalate, polyethylene dynaphate, terephthalic acid? 1,4-butanedi All polybutylene ether co-condensation elastomer, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, liquid crystalline polymer compound, cellulose acetate, etc. It is not limited to these.

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

When the organophosphorus-nitrogen compound of the present invention is used as a flame retardant, the content thereof varies greatly depending on the type of polymer resin to be blended and the target flame retardant performance. It may be included, preferably 1 to 40 parts by weight, more preferably 5 to 20 parts by weight. When included in less than 1 part by weight is not sufficient to improve the flame retardancy, when included in excess of 60 parts by weight is not preferable because the physical properties of the resin due to excessive addition changes.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example  1> Oxazolinones  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1a)

A 2 L volume round bottom three necked flask equipped with a reflux cooler and a dropping funnel was installed and 2-benzoxazoline (1.01 mol, 136.5 g), triethylamine (0.92 mol, 93 g) and tetrahydrofuran as solvent 700 ml) was added and stirred at room temperature to completely dissolve the solids. Subsequently, after dropping phosphorus oxychloride (0.31 mol, 50 g) over about 1 hour using a dropping funnel at room temperature, the reaction solution was reacted at room temperature (25 ° C.) for about 24 hours. After the reaction was completed, the resulting suspension was filtered, the solvent of the filtrate was removed, washed several times with a large amount of isopropyl alcohol, and dried to obtain 100 g of a compound of Formula 1a.

Mass spectrometry and thermal properties were evaluated on the prepared compounds of Formula 1a using gas chromatography-mass spectrometry (GC-MS; JEOL.JMS-600) and differential scanning calorimetry (DSC; METTLER TOLEDO / DSC 823e). , The mass spectrometry results are shown in FIG. 1, and the thermal characteristics evaluation results are shown in FIG. 2, respectively.

As shown in Figure 1, it was confirmed by mass spectrometry that the molecular weight of the compound of Formula 1a is 449, as shown in Figure 2, through the thermal analysis it was confirmed that the melting point of the compound of Formula 1a is 244 ~ 245 ℃ .

< Example  2> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1b)

A 2 L volume round bottom three necked flask equipped with a reflux cooler and a dropping funnel was installed and 2-benzoxazoline (0.95 mol, 128 g) triethylamine (0.95 mol, 96 g) and tetrahydrofuran (700) as solvent. ml) was added and stirred at room temperature to completely dissolve the solids. Thereafter, phenyl dichlorophosphate (0.47 mol, 100 g) was added dropwise over about 2 hours using a dropping funnel at room temperature, and the reaction solution was reacted at 40 ° C. for about 24 hours. After the reaction was terminated, the resulting suspension was filtered and the obtained solid was washed several times with a large amount of water and dried to give 154 g of the compound of formula 1b.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1b was 408, and it was confirmed that the melting point of the compound of Formula 1b was 118 ° C.

< Example  3> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1c)

A 2 L volume round bottom three necked flask equipped with a reflux cooler and a dropping funnel was installed and 2-benzoxazoline (0.82 mol, 111 g) triethylamine (0.82 mol, 83 g) and tetrahydrofuran (600) as solvent. ml) was added and stirred at room temperature to completely dissolve the solids. Thereafter, phenylphosphonic dichloride (0.41 mol, 80 g) was added dropwise over about 2 hours using a dropping funnel at room temperature, and the reaction solution was reacted at 40 ° C. for about 24 hours. After the reaction was completed, the resulting suspension was filtered, the filtrate was extracted with distilled water and ethyl acetate, and the obtained solid was washed several times with a large amount of water to obtain 120 g of a compound of Formula 1c.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1c was 392, and it was confirmed that the melting point of the compound of Formula 1c was 152 ° C.

< Example  4> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1d)

A 1 L volume round bottom three-necked flask equipped with a reflux cooler and a dropping funnel was installed and 2-oxazoline (0.72 mol, 62.5 g) triethylamine (0.72 mol, 73 g) and tetrahydrofuran (400 ml) as solvent. ) And stirred at room temperature to completely dissolve the solids. Subsequently, phenylphosphonic dichloride (0.36 mol, 70 g) was added dropwise over about 2 hours using a dropping funnel at room temperature, and the reaction solution was reacted at 40 ° C. for about 24 hours. After the reaction was completed, the resulting suspension was filtered, the filtrate was extracted with distilled water and ethyl acetate, and the obtained solid was washed several times with a large amount of 1 normal hydrochloric acid solution to obtain 84 g of a compound of formula 1d.

It was confirmed by mass spectrometry that the molecular weight of the compound of Formula 1d was 296, and the melting point of the compound of Formula 1d was 105 ° C.

< Example  5> Oxazolinones  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1e)

A compound of Formula 1e was obtained by the same method as Example 4 except for using 1,3-phenylene diphosphorodichlorate instead of phenylphosphonic dichloride.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1e was 546, and it was confirmed that the melting point of the compound of Formula 1e was 101 ° C.

< Example  6> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1f)

A compound of Formula 1f was obtained by the same method as Example 4 except for using 1,3-phenylene bis (methylphosphonochlorate) instead of phenylphosphonic dichloride.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1f was 404, and it was confirmed that the melting point of the compound of Formula 1f was 88 ° C.

< Example  7> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1g)

A compound of Formula 1 g was obtained by the same method as Example 4 except for using the compound of Formula A instead of phenylphosphonic dichloride.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1g was 787, and it was confirmed that the melting point of the compound of Formula 1g was 137 ° C.

< Example  8> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1h)

The compound of Formula 1h was obtained by the same method as Example 4 except for using the compound of Formula B instead of phenylphosphonic dichloride.

Mass spectrometry confirmed that the molecular weight of the compound of Formula 1h was 794, and the melting point of the compound of Formula 1h was 171 ° C.

< Example  9> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1i)

The compound of Formula 1i was obtained by the same method as Example 4 except for using the compound of Formula C instead of phenylphosphonic dichloride.

It was confirmed that the melting point of the compound of Formula 1i was 132 ° C.

< Example  10> Oxazolinone  With derivatives Organic phosphorus Preparation of Nitrogen-Based Compound (Formula 1j)

A compound of Formula 1j was obtained by the same method as Example 4 except for using the compound of Formula D instead of phenylphosphonic dichloride.

It was confirmed that the melting point of the compound of Formula 1j was 127 ° C.

< Example  11> in accordance with the present invention Flame retardant  Preparation of the composition

Flame retardant composition was prepared by the following method for flame retardancy evaluation using the compound of the present invention.

40 parts by weight of the compound of formula 1a prepared in Example 1 as a flame retardant, 0.1 part by weight of anti-dripping polytetrafluoroethylene (PTEE), and 5 parts of synergist, zinc borate. Each part was added to a stirrer (uniaxial mixer) having a content of 1 kg, stirred for 10 minutes, and preliminarily dispersed to obtain a uniform flame retardant mixture (preliminary mixing step). At this time, the rotation speed of the stirring blade which a stirrer had was set to 2000 rpm.

Next, a flame retardant mixture obtained by the premixing process was added to 100 parts by weight of polystyrene resin HIPS (weight average molecular weight (Mw): 100,000, BASF company LTD) and the temperature range of 200 to 260 ° C. in a Brabender Mixer. A flame retardant composition was prepared by mixing in a range of 5 to 20 minutes at a rotation speed of 60 rpm at.

< Example  12> in accordance with the present invention Flame retardant  Preparation of the composition

A flame retardant composition was prepared in the same manner as in Example 11, except that 20 parts by weight of the compound of Formula 1a prepared in Example 1 was added as a flame retardant.

< Example  13> According to the present invention Flame retardant  Preparation of the composition

A flame retardant composition was prepared in the same manner as in Example 11, except that 20 parts by weight of the compound of Formula 1a prepared in Example 1 as a flame retardant and 1 part by weight of apatite instead of zinc borate were added as synergists.

< Comparative example  1> according to the prior art Flame retardant  Preparation of the composition

As a conventional flame retardant, a compound having the following formula (SP-703 manufactured by Shikoku Chemical Co., Ltd.) was prepared.

Next, a flame retardant composition was prepared in the same manner as in Example 11 except that 100 parts by weight of the polystyrene resin HIPS powder and 20 parts by weight of the flame retardant SP-703 were added.

< Experimental Example  1> Flame retardancy rating

The following method was performed to evaluate the flame retardancy of the compound according to the present invention.

<1-1> Specimen Preparation

Flame retardant evaluation specimens were prepared by molding the flame retardant composition prepared in Examples 11 to 13 and Comparative Example 1 for 3 to 30 minutes at an temperature range of 170 to 240 ° C. with an extruder. At this time, the specimens were manufactured in a size of 6.5 × 70 × 3 mm ³ , five specimens were prepared for each sample.

<1-2> flame retardancy evaluation

Flame retardancy evaluation was performed using the UL-94V test method established by the US Underwriters Laboratories.

When evaluating the flame retardancy of the manufactured specimens, the test standard is adjusted to 20 mm according to IEC 60695-11-10 using small flames (50 W), and the burner is removed from the bottom of the specimen by 10 mm. It was positioned mm apart. The specimen was set up, fired for 10 seconds with a burner, the burner was removed, and the time t1 until the fire on the specimen was extinguished was measured and the flame retardant rating was evaluated from these results.

First, the flame retardant grade of V-0 is given when t1 of the specimen is less than 10 seconds, and the flame retardant grade of V-1 is given when t1 is less than 30 seconds and no spalling by fire occurs. The flame retardancy rating is given when t1 is less than 30 seconds and spitting occurs by fire.

The measurement results are shown in Table 2 below.

Example 11 Example 12 Example 13 Comparative Example 1
Creation costs
HIPS: Formula 1a
= 100: 40
HIPS: Formula 1a
= 100: 20 HIPS: Formula 1a + apatite
= 100: 20 + 1
HIPS: SP703
= 100: 20 t1 15.3 25.7 21.8 27 Flame Retardant Grade V-1 V-1 V-1 V-2

As a result of the measurement, as shown in Table 1, in the compositions according to the present invention (Examples 11 to 13), t1 was 15.3, 25.7, and 21.8 seconds, respectively, and both were not ignited by fire, so that the flame retardant grade was V-. Rated one. On the other hand, in the case of the flame retardant of the prior art (Comparative Example 1), t1 was measured as 27 seconds, but ignition due to sparking occurred, and the flame retardant grade was measured as V-2.

From the above experimental results, the composition including the organophosphorus-nitrogen compound according to the present invention was found to have excellent flame retardancy compared to the conventional organophosphorus compound.

Therefore, the composition containing the organophosphorus-nitrogen compound according to the present invention does not contain a halogen element, which is environmentally friendly, excellent in heat resistance and water resistance, excellent in stability, and simultaneously contains phosphorus and nitrogen, and particularly includes oxazolinone. It is excellent in flame retardancy because carbon dioxide is generated during combustion decomposition can be usefully used as a flame retardant of various polymer resins.

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)

Phosphorus-nitrogen flame retardant compound containing an oxazolinone derivative represented by Formula 1:
[Formula 1]

(In Formula 1,
R ¹ and R ² are hydrogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C ₁ to C ₁₀ straight or branched chain alkyl, C ₂ to C ₁₀ straight chain Or branched alkenyl, C ₂ to C ₁₀ straight or branched alkynyl, C ₁ to C ₁₀ alkoxy, C ₃ to C ₁₀ cycloalkyl, C ₆ to C ₁₀ aryl, 5 to 10 membered heteroaryl, Or a C ₆ to C ₁₀ aryloxy group or C ₇ to C ₁₀ arylalkyl, wherein R ¹ and R ² may be unsubstituted or substituted with the aforementioned substituents;
Oz is an oxazolinone derivative substituent selected from the group consisting of the following substituents;

,
Wherein R ³ to R ⁸ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group;
L is nitrogen, oxygen, sulfur, phosphorus or carbonyl, silyl, boranyl, C ₁ to C ₁₀ straight or branched chain alkyl, C ₂ to C ₁₀ straight or branched alkenyl, C ₂ to C ₁₀ straight chain Or a side chain alkynyl, C ₁ to C ₁₀ alkoxy, C ₃ to C ₁₀ cycloalkyl, C ₆ to C ₁₀ aryl, 5 to 10 membered heteroaryl, or C ₆ to C ₁₀ aryloxy group , Wherein L may be unsubstituted or substituted with substituents defined in R ¹ and R ² ;
X is oxygen, sulfur or selenium;
Y ¹ is R ₁ or Oz;
Y ² is R ¹ , R ² or Oz;
l is 1 or 2;
m is 1 or 2;
n is an integer from 0 to 10;
y is 0 or 1;
l is 1 when n and y are 0,
If y is 1 then Y ¹ is Oz and l is m.)
The phosphorus-nitrogen flame retardant compound of claim 1, wherein the phosphorus-nitrogen flame retardant compound of Formula 1 is selected from the group consisting of compounds represented by the following Formulas 2 to 4.
(2)

(3)

[Chemical Formula 4]

(In Chemical Formulas 2 to 4,
R ¹ , R ² , X, Y ² , L and Oz are as defined in Formula 1 of claim 1,
a is an integer of 1 to 3,
b is an integer of 1 to 2.)
The phosphorus-nitrogen flame retardant compound according to claim 2, wherein L is selected from the group consisting of the following substituents.

The method of claim 1, wherein the phosphorus-nitrogen compound of Formula 1 is
(1) 3,3 ', 3''-phosphoryltribenzo [d] oxazol-2 (3H) -one;
(2) phenyl bis (2-oxobenzo [d] oxazol-3 (2H) -yl) phosphinate;
(3) 3,3 '-(phenylphosphoryl) dibenzo [d] oxazol-2 (3H) -one;
(4) 3,3 '-(phenylphosphoryl) dioxazolidin-2-one;
(5) 1,3-phenylene bis (bis (2-oxooxazolidin-3-yl) phosphinate;
(6) 1,3-phenylene bis (methyl (2-oxooxazolidin-3-yl) phosphinate);
(7) bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) 2-oxooxazolidin-3-ylphosphonate;
(8) bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) phenyl phosphate;
(9) 1,3-phenylene bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) bis (2-oxooxazolidin-3-ylphosphonate); And
(10) oxazolinones selected from the group consisting of 1,3-phenylene bis (3- (bis (2-oxooxazolidin-3-yl) phosphoryloxy) phenyl) diphenyl diphosphate Phosphorus-nitrogen flame retardant compound containing derivatives.
As shown in Scheme 1 below,
A method for preparing a phosphorus-nitrogen flame retardant compound containing the oxazolinone derivative comprising the step of reacting an oxazolinone derivative compound with a compound of Formula 5 in a solvent to prepare a compound of Formula 1.
[Reaction Scheme 1]

(In Scheme 1,
R ¹ , R ² , Oz, X, Y ¹ , Y ² , L, m, n, y and l are as defined in Formula 1 of claim 1,
Z is a halogen or hydroxy group
Z ¹ is Z or R ^1. )
The oxazolinone derivative according to claim 5, wherein the oxazolinone derivative (Oz-H) is 2-oxazolinone or 2-benzoxazolinone. Process for producing phosphorus-nitrogen based flame retardant compound.
The method of claim 5, wherein the phosphorus-containing reactive compound of formula 5 is diphenylchlorophosphate, diphenyl phosphate, diphenylphosphonic chloride, phenylphosphonic dichloride, phenyl dichlorophosphate phosphorus oxychloride, phenylene di Phosphorodichlorate, phenylene bis (methylphosphonochloridate), chlorophosphorylbis (oxy) bis (3,1-phenylene) diphosphorodichlorate, phenoxyphosphorylbis (oxy A method for producing a phosphorus-nitrogen flame retardant compound containing an oxazolinone derivative, characterized in that it is selected from the group consisting of bis (3,1-phenylene) diphosphorodichlorate.
The method of claim 5, wherein the Oz-H compound is used in an amount of 1 to 5 equivalents based on 1 equivalent of the compound of Formula 5, wherein the phosphorus-nitrogen-based flame retardant compound is prepared.
6. The phosphorus-nitrogen-based system comprising an oxazolinone derivative according to claim 5, wherein the solvent is any one selected from the group consisting of chloroform, tetrahydrofuran, dimethylformamide, distilled water, and a mixed solvent thereof. Method for producing a flame retardant compound.
The method according to claim 5, wherein any one base selected from the group consisting of triethylamine, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and sodium hydroxide is further used in terms of improving reaction yield and shortening reaction time. Method for producing a phosphorus-nitrogen flame retardant compound containing an oxazolinone derivative, characterized in that.
The method of claim 10, wherein the base is used in an amount of 1 to 10 mol based on 1 equivalent of the compound of Formula 5.
A flame retardant composition in which a phosphorus-nitrogen flame retardant compound containing the oxazolinone derivative of claim 1 and a polymer resin are mixed.
The method of claim 12, wherein the polymer resin is polyethylene, polypropylene, polybutylene, polyisobutylene, polybutadiene, polyacrylonitrile, polystyrene, styrene butadiene copolymer, acrylonitrile butadiene Ethylene copolymer, styrene acrylonitrile copolymer, ABS resin, polyacetal, polyphenyl oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene dynaphthoate, terephthalic acid? 1,4-butanediol-polybutylene ether co-condensation elastomer, polycarbonate, polyamide, polyimide, polyurethane, epoxy resin, phenol resin, melamine resin, urea resin, liquid crystalline high molecular compound and cellulose acetate Flame retardant composition, characterized in that selected from the group.
The flame retardant composition according to claim 12, wherein the compound of Formula 1 is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the polymer resin.

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