KR20220060745A - Organophosphorus compound, method of manufacturing the same and flame retardant composition comprising the same - Google Patents

Abstract

The present invention relates to an organophosphorus compound, method for preparing the same and a flame retardant composition including the same. Particularly, the present invention relates to an organophosphorus compound represented by chemical formula 1, method for preparing the same, and a flame retardant composition prepared by impregnating and blending silica with the compound to prevent migration, to ensure processability and to provide improved hardness and mechanical strength. In chemical formula 1, each of R_1 and R_2 independently represents H, a C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 aryloxy group, C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group; and R_3 represents a C1-C15 alkyl group, C6-C20 aryl group, C1-C10 alkyl-substituted C6-C20 aryl group or C6-C20 aralkyl group.

Description

An organophosphorus compound, a method for manufacturing the same, and a flame retardant composition comprising the same

The present invention relates to an organophosphorus compound, a method for preparing the same, and a flame retardant composition comprising the same, and more particularly, to a novel organophosphorus compound, a method for preparing the compound, and a method for preparing the compound by impregnating the compound with silica and mixing the compound to prevent migration and improve processability It is possible to secure and relates to a flame retardant composition having improved hardness and mechanical strength.

Recently, as the use of plastics has been broadly expanded to construction, automobiles, electrical appliances, aircraft, ships, etc., the need for flame retardants in consideration of safety in case of fire is continuously increasing.

Since most plastics are organic substances composed of carbon, hydrogen and oxygen, they have the property of being easily combusted.

These flame retardants should have good compatibility with raw materials and additives, should not affect the mechanical properties of the final product, and should generate less smoke and toxic gas during combustion.

The plastic flame retardant method includes: first, the production of heat-resistant plastic through molecular structure change, second, chemically bonding the flame-retardant component into the plastic structure (reactive flame retardant), third, physically adding the flame retardant into the plastic (additive type) flame retardant), fourth, coating or painting with other flame retardants, or promoting heat resistance improvement through product design change, and the use of an additive type flame retardant is a typical known method.

On the other hand, phosphorus-based flame retardants are currently attracting attention as an alternative to halogen-based flame retardants, and representative phosphorus-based flame retardants include red phosphorus, phosphate ester or phosphate, phosphinate, phosphine oxide, phosphazene. ), etc.

Phosphine (PH3), a compound made only of phosphorus, is used limitedly due to the possibility of generation of phosphine (PH3) during processing or is used with surface coating. have it

The most applied structure is phosphate, and according to the flame retardant mechanism, phosphorus-based flame retardants differ from halogen-based flame retardants in that the flame retardant effect in the solid phase is important. It is difficult to impart flame retardancy to the polymer itself.

However, the phosphate-based flame retardant has a stable chemical structure and has an effect of imparting plasticity, thereby facilitating the processing of the flame-retardant resin and having good compatibility and weather resistance, but has a disadvantage in that heat resistance is lowered.

In addition, the phosphinate-based flame retardant has a strong structural polarity, and when the molecular weight is not large, it is often water-soluble, so there is a limitation in application as a flame retardant of an organic polymer resin, and there is a disadvantage in that the manufacturing cost is relatively high compared to phosphate.

Republic of Korea Patent Publication No. 10-2018-0100333 (published on September 10, 2018) Republic of Korea Patent Publication No. 10-2017-0037860 (published on April 5, 2017) Republic of Korea Patent Publication No. 10-2012-0030331 (published on March 28, 2012)

The present invention has been devised to solve the problems of the prior art as described above, and an object of the present invention is to provide a novel phosphonate-based organophosphorus compound.

Another object of the present invention is to provide a method for preparing the phosphonate-based novel organophosphorus compound.

Another object of the present invention is to provide a flame retardant composition with improved hardness and mechanical strength, which can prevent migration and processability by including the phosphonate-based novel organophosphorus compound.

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

[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group; R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

The present invention also provides an organophosphorus compound wherein the organophosphorus compound is bis((diethoxyphosphoryl)methyl)phenylphosphonate [bis((diethoxyphosphoryl)methyl phenylphosphonate)] represented by the following Chemical Formula 1a.

[Formula 1a]

The present invention also provides a method for preparing an organophosphorus compound represented by the following formula (1) by condensing a compound represented by the following formula (2) and a compound represented by the following formula (3).

[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group; R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

[Formula 2]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.

[Formula 3]

In the above formula, R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

The present invention also provides a method for preparing an organophosphorus compound prepared by condensing a compound represented by Formula 2 with a compound represented by Formula 4 and a compound represented by Formula 5 below.

[Formula 4]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.

[Formula 5]

The present invention also provides a method for preparing an organophosphorus compound wherein the organophosphorus compound represented by Compound 1 is bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by the following Chemical Formula 1a.

[Formula 1a]

The present invention also provides a method for preparing an organophosphorus compound wherein the compound represented by Formula 2 is diethyl (hydroxymethyl) phosphonate represented by Formula 2a below.

[Formula 2a]

The present invention also provides a method for preparing an organophosphorus compound wherein the compound represented by Chemical Formula 3 is phenylphosphonic dichloride represented by the following Chemical Formula 3a.

[Formula 3a]

The present invention also provides a method for preparing an organophosphorus compound in which the compound represented by Formula 4 is diethyl phosphite represented by Formula 4a below.

[Formula 4a]

The present invention also provides a method for preparing an organophosphorus compound in which the compound represented by Formula 2 and the compound represented by Formula 3 are reacted in a molar ratio of 2-3.

The present invention also provides a method for preparing an organophosphorus compound in which the compound represented by Formula 2 and the compound represented by Formula 3 are reacted in a molar ratio of 2.4:1.

In the present invention, the condensation is water, dichloromethane, C1-C4 anhydrous or hydrous lower alcohol, propylene glycol, butylene glycol, glycerin, acetone, ethyl acetate, chloroform, butyl acetate, diethyl ether, hexane and mixtures thereof. It provides a method for preparing an organophosphorus compound carried out in any one solvent selected from the group consisting of.

The present invention also provides a method for preparing an organophosphorus compound wherein the condensation is carried out in the presence of a triethylamine catalyst.

The present invention also provides a method for preparing an organophosphorus compound in which the compound represented by Formula 4 and the compound represented by Formula 5 are reacted in a molar ratio of 1:1 to 2.

The present invention also provides a method for preparing an organophosphorus compound in which the compound represented by Formula 4 and the compound represented by Formula 5 are reacted in a molar ratio of 1:1.5.

The present invention also provides a flame retardant composition comprising the organophosphorus compound.

The present invention also provides a flame retardant composition wherein the flame retardant composition further comprises at least one selected from the group consisting of ethylene propylene rubber (EPDM), silica, graphite, and melamine-based flame retardants.

The present invention also provides a flame retardant composition wherein the melamine-based flame retardant is at least one selected from the group consisting of melamine cyanurate, melamine phosphate, melamine borate and melamine metal phosphate.

The present invention also provides a flame retardant composition wherein the phosphorus content in the flame retardant composition is 1.2 to 4.3% by weight.

The present invention also provides a flame retardant composition comprising 3 to 7 parts by weight of the silica, 10 to 20 parts by weight of the graphite, and 10 to 20 parts by weight of the melamine-based flame retardant with respect to 100 parts by weight of the ethylene propylene rubber.

The present invention also has a tensile strength of 10 to 50 of the flame retardant composition A flame retardant composition of kg/cm 2 is provided.

The present invention also provides a flame retardant composition in which the flame retardant composition has a flame retardancy rating of V-0 as a result of the UL-94 vertical flame retardancy test method.

According to the present invention, by impregnating the organophosphorus compound with silica and blending it, migration prevention and processability can be secured, and a flame retardant composition having improved hardness and mechanical strength can be provided, so it does not contain a halogen element, so it does not contain a halogen element. There is an advantage that can provide a friendly flame retardant composition.

1A to 1C are photographs sequentially illustrating a process for preparing diethyl (hydroxymethyl) phosphonate (DEHMP) of Scheme 1a according to an embodiment of the present invention.
2A to 2E are photographs sequentially illustrating a process for preparing bis((diethoxyphosphoryl)methyl)phenylphosphonate of Scheme 2a according to an embodiment of the present invention.
3A shows ¹ H-NMR and ³¹ P-NMR spectra of diethyl (hydroxymethyl) phosphonate (DEHMP) prepared according to Scheme 1a according to an embodiment of the present invention.
3B shows ¹ H-NMR and ³¹ P-NMR spectra of bis((diethoxyphosphoryl)methyl)phenylphosphonate prepared according to Scheme 2a according to an embodiment of the present invention.

It should be noted that, in the following description, only the parts necessary for understanding the embodiments of the present invention will be described, and descriptions of other parts will be omitted in the scope not disturbing the gist of the present invention.

The terms or words used in the present specification and claims described below should not be construed as being limited to their ordinary or dictionary meanings, and the inventors have appropriate concepts of terms to describe their invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined in Accordingly, the embodiments described in this specification and the configurations shown in the drawings are only preferred embodiments of the present invention, and do not represent all of the technical spirit of the present invention, so various equivalents that can be substituted for them at the time of the present application It should be understood that there may be variations and variations.

Hereinafter, the present invention will be described in detail.

A first embodiment of the present invention relates to an organophosphorus compound represented by the following formula (1).

[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group; R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

The C1-C15 alkyl group of R ₁ to R ₃ may be linear, branched or cyclic, and more preferably have 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group , 2-methylbutyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group , isoheptyl group, octyl group, isooctyl group, 2,2,5-trimethylpentyl group, 2-ethylhexyl group, nonyl group, isononyl group, n-decyl group, isodecyl group, such as linear or branched form shape of an alkyl group; Cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, 2,5-dimethylcyclohexyl group, 2-isopropyl-5-methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclono A cyclic alkyl group such as a nyl group or a cyclodecyl group may be exemplified, but the present invention is not limited thereto.

The C6-C20 aryl group of R ₁ to R ₃ may include, but is not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and a biphenyl group.

Examples of the C7-C15 or C6-C20 aralkyl group of R ₁ to R ₃ include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, and a phenyloctyl group. may be mentioned, but is not limited thereto.

Examples of the C7-C15 alkylaryl group of R ₁ to R ₃ include tolyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, xylyl group, etc. For example, but is not limited thereto.

The C1-C15 alkoxy group for R ₁ to R ₂ may be any of linear, branched or cyclic, and more preferably have 1 to 10 carbon atoms. Specifically, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentylox group group, 1-methylbutoxy group, 2-methylbutoxy group, tert-pentyloxy group, neopentyloxy group, 1,2-dimethylpropyloxy group, 1-ethylpropyloxy group, 2-ethylpropyloxy group, n -Hexyloxy group, isohexyloxy group, n-heptyloxy group, isoheptyloxy group, octyloxy group, isooctyloxy group, 2,2,5-trimethylpentyloxy group, 2-ethylhexyloxy group, no linear or branched alkoxy groups such as nyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group; Cyclopentyloxy group, cyclohexyloxy group, cyclohexylmethoxy group, 2-cyclohexylethoxy group, 2,5-dimethylcyclohexyloxy group, 2-isopropyl-5-methylcyclohexyloxy group, cycloheptylox A cyclic alkoxy group such as a group, a cyclooctyloxy group, a cyclononyloxy group, and a cyclodecyloxy group may be exemplified, but the present invention is not limited thereto.

Examples of the aryloxy group of R ₁ to R ₂ include, but are not limited to, a phenoxy group, a naphthoxy group, a phenanthryloxy group, an anthracenyloxy group, and a biphenyloxy group.

Examples of the C7-C15 aralkyloxy group represented by R ₁ to R ₂ include benzyloxy group, phenethyloxy group, phenylpropyloxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenylox group A tyloxy group may be exemplified, but the present invention is not limited thereto.

As the C7-C15 alkylaryloxy group of R ₁ to R ₂ , tolyloxy group, ethylphenoxy group, n-propylphenoxy group, iso-propylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert- A butylphenoxy group, a xylyloxy group, and the like may be exemplified, but the present invention is not limited thereto.

Among the organophosphorus compounds of the present invention, R ₁ and R ₂ are preferably a hydrogen atom or a C1-C15 alkyl group, more preferably a methyl group, but is not limited thereto.

In addition, as R ₃ , preferably, a C1-C15 alkoxy group, a phenyl group, a phenoxy group, and more preferably a phenyl group can be mentioned, but is not limited thereto.

The organophosphorus compound of the present invention is characterized by a relatively low melting point and a high phosphorus content. The melting point of the organophosphorus compound of the present invention is preferably 130 to 250°C, more preferably 135 to 200°C, still more preferably 140 to 190°C.

In addition, the phosphorus content of the organophosphorus compound of the present invention preferably exceeds 10 mass%, more preferably 12 mass% or more, but is not limited thereto.

Among the organophosphorus compounds represented by Formula 1, preferred compounds include bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by Formula 1a below, as shown in FIG. 3b , but limited thereto. it is not going to be

[Formula 1a]

A second embodiment of the present invention relates to a method for preparing an organophosphorus compound represented by the following Chemical Formula 1 by condensing a compound represented by the following Chemical Formula 2 and a compound represented by the following Chemical Formula 3, as shown in Scheme 1 below. .

[Scheme 1]

[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group; R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

[Formula 2]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.

[Formula 3]

In the above formula, R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.

In the method for producing an organophosphorus compound according to the second embodiment, the C1-C15 alkyl group of R ₁ to R ₃ may be any of linear, branched, or cyclic, and it is more preferable that the C1-C15 alkyl group has 1 to 10 carbon atoms. desirable. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 1-methylbutyl group , 2-methylbutyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group , isoheptyl group, octyl group, isooctyl group, 2,2,5-trimethylpentyl group, 2-ethylhexyl group, nonyl group, isononyl group, n-decyl group, isodecyl group, such as linear or branched form shape of an alkyl group; Cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, 2,5-dimethylcyclohexyl group, 2-isopropyl-5-methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclono A cyclic alkyl group such as a nyl group or a cyclodecyl group may be exemplified, but the present invention is not limited thereto.

The C6-C20 aryl group of R ₁ to R ₃ may include, but is not limited to, a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and a biphenyl group.

Examples of the C7-C15 or C6-C20 aralkyl group of R ₁ to R ₃ include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, and a phenyloctyl group. may be mentioned, but is not limited thereto.

Examples of the C7-C15 alkylaryl group of R ₁ to R ₃ include tolyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, xylyl group, etc. For example, but is not limited thereto.

The C1-C15 alkoxy group for R ₁ to R ₂ may be any of linear, branched or cyclic, and more preferably have 1 to 10 carbon atoms. Specifically, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentylox group group, 1-methylbutoxy group, 2-methylbutoxy group, tert-pentyloxy group, neopentyloxy group, 1,2-dimethylpropyloxy group, 1-ethylpropyloxy group, 2-ethylpropyloxy group, n -Hexyloxy group, isohexyloxy group, n-heptyloxy group, isoheptyloxy group, octyloxy group, isooctyloxy group, 2,2,5-trimethylpentyloxy group, 2-ethylhexyloxy group, no linear or branched alkoxy groups such as nyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group; Cyclopentyloxy group, cyclohexyloxy group, cyclohexylmethoxy group, 2-cyclohexylethoxy group, 2,5-dimethylcyclohexyloxy group, 2-isopropyl-5-methylcyclohexyloxy group, cycloheptylox A cyclic alkoxy group such as a group, a cyclooctyloxy group, a cyclononyloxy group, and a cyclodecyloxy group may be exemplified, but the present invention is not limited thereto.

Examples of the aryloxy group of R ₁ to R ₂ include, but are not limited to, a phenoxy group, a naphthoxy group, a phenanthryloxy group, an anthracenyloxy group, and a biphenyloxy group.

Examples of the C7-C15 aralkyloxy group represented by R ₁ to R ₂ include benzyloxy group, phenethyloxy group, phenylpropyloxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenylox group A tyloxy group may be exemplified, but the present invention is not limited thereto.

As the C7-C15 alkylaryloxy group of R ₁ to R ₂ , tolyloxy group, ethylphenoxy group, n-propylphenoxy group, iso-propylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert- A butylphenoxy group, a xylyloxy group, and the like may be exemplified, but the present invention is not limited thereto.

In Scheme 1, the reaction may be carried out in the presence of a catalyst, and as the catalyst, an alkali metal hydroxide catalyst, an alkaline earth metal hydroxide catalyst, a tin-based catalyst, an amine-based catalyst, etc. may be used, preferably an amine-based catalyst, More preferably, triethylamine (TEA) may be mentioned, but is not limited thereto.

In the method for preparing an organophosphorus compound according to the second embodiment, the compound represented by Formula 2 is a compound represented by Formula 4 and a compound represented by Formula 5 below, as shown in Scheme 2 below, by condensing can be manufactured.

[Scheme 2]

[Formula 4]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.

[Formula 5]

Since R ₁ and R ₂ are the same as described above, a detailed description thereof will be omitted.

In Scheme 2, the reaction may be carried out in the presence of a catalyst, and as the catalyst, an alkali metal hydroxide catalyst, an alkaline earth metal hydroxide catalyst, a tin-based catalyst, an amine-based catalyst, etc. may be used, preferably an amine-based catalyst, More preferably, triethylamine (TEA) may be mentioned, but is not limited thereto.

In the method for preparing the organophosphorus compound of the present invention, the organophosphorus compound represented by Compound 1 may be preferably bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by the following Chemical Formula 1a. , but is not limited thereto.

[Formula 1a]

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Formula 2 may be preferably diethyl (hydroxymethyl) phosphonate represented by Formula 2a, but is not limited thereto. .

[Formula 2a]

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Chemical Formula 3 may preferably be an organophosphorus compound represented by the following Chemical Formula 3a, which is phenylphosphonic dichloride, but is not limited thereto.

[Formula 3a]

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Formula 4 may be preferably diethyl phosphite represented by Formula 4a, but is not limited thereto.

[Formula 4a]

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Formula 2 and the compound represented by Formula 3 may be reacted in a molar ratio of 2 to 3:1, but the present invention is not limited thereto.

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Formula 2 and the compound represented by Formula 3 may be reacted in a molar ratio of 2.4:1, but the present invention is not limited thereto.

In the method for preparing the organophosphorus compound of the present invention, the condensation is water, dichloromethane, C1-C4 anhydrous or hydrous lower alcohol, propylene glycol, butylene glycol, glycerin, acetone, ethyl acetate, chloroform, butyl acetate, di It may be any one solvent selected from the group consisting of ethyl ether, hexane, and mixtures thereof, preferably chloroform, but is not limited thereto.

In the method for preparing the organophosphorus compound of the present invention, the compound represented by Formula 4 and the compound represented by Formula 5 are reacted in a molar ratio of 1:1 to 2 to prepare the compound represented by Formula 2 However, the present invention is not limited thereto.

In the method for preparing the organophosphorus compound of the present invention, preferably, the compound represented by the formula (4) and the compound represented by the formula (5) are reacted in a molar ratio of 1: 1.5 to prepare the compound represented by the formula (2) can, but is not limited thereto.

A third embodiment of the present invention relates to a flame retardant composition comprising the organophosphorus compound according to the first embodiment.

The flame retardant composition of the present invention may further include one or more selected from the group consisting of ethylene propylene rubber (EPDM), silica, graphite, and melamine-based flame retardants, but is not limited thereto.

The flame retardant composition of the present invention may further include ethylene propylene rubber (EPDM), silica, graphite (graphite), and a melamine-based flame retardant, but is not limited thereto.

The melamine-based flame retardant that may be included in the flame retardant composition of the present invention may be melamine cyanurate, melamine phosphate, melamine borate and/or melamine metal phosphate, but is not limited thereto.

The melamine-based flame retardant that may be included in the flame retardant composition of the present invention may be preferably melamine cyanurate or melamine phosphate, but is not limited thereto.

In the flame retardant composition of the present invention, in addition to the above components, stabilizers, plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, other flame retardants, antistatic agents, foaming agents, anti-drip agents (eg PTFE), fillers and / or a reinforcing agent may be further included, but is not limited thereto.

The filler and reinforcing agent may include, but are not limited to, calcium carbonate, silicate, glass fiber, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, and the like.

The fillers and adjuvants may be present in relatively high concentrations, including formulations in which the fillers or adjuvants are present in concentrations greater than 50% by weight, based on the weight of the final composition. More typically, the fillers and reinforcing agents may be present in an amount of from 5% to 50% by weight, for example from 10% to 40% or from 15% to 30% by weight, based on the weight of the total polymer composition.

The phosphorus content in the flame retardant composition of the present invention may be 1.2 wt% or more, preferably 1.2 to 4.3 wt%, more preferably 1.2 to 1.8 wt%, but is not limited thereto.

The flame retardant composition of the present invention may include 3 to 7 parts by weight of the silica, 10 to 20 parts by weight of the graphite, and 10 to 20 parts by weight of the melamine cyanurate based on 100 parts by weight of the ethylene propylene rubber, but limited thereto it is not going to be

Preferably, the flame retardant composition of the present invention may include 4 to 6 parts by weight of the silica, 13 to 17 parts by weight of the graphite, and 13 to 17 parts by weight of the melamine cyanurate, based on 100 parts by weight of the ethylene propylene rubber. there is.

The flame retardant composition of the present invention is more preferably, based on 100 parts by weight of the ethylene propylene rubber, 4 to 6 parts by weight of the silica, 14 to 16 parts by weight of the graphite, and 14 to 16 parts by weight of the melamine cyanurate. can

Tensile strength of the flame retardant composition according to the present invention is 10 to 50 kg/cm2, preferably 40-50 It may be kg/cm 2 , but is not limited thereto.

The hardness (20.5 ℃, type A) of the flame retardant composition according to the present invention may be 70 or more, preferably 73 to 76, but is not limited thereto.

The elongation of the flame retardant composition according to the present invention may be 900% or more, preferably 930 to 1000, more preferably 940 to 990, but is not limited thereto.

The tear strength of the flame retardant composition according to the present invention may be 7 kg / cm or more, preferably 7 ~ 9 kg / cm, more preferably 7.2 ~ 8.6 kg / cm, but limited thereto not.

The flame retardant composition according to the present invention has a flame retardancy of V-0 grade as a result of UL-94 vertical flame retardancy test method.

The UL-94 vertical flame retardant test method (UL 94 V Test: Vertical Burning Test) is a test method for evaluating the combustion aspect of the product and the degree of flame propagation to the surroundings when a flame is applied in the vertical direction of the plastic product.

The UL-94 vertical flame-retardant test method is ① after contacting a 20 mm-long flame to the specimen for 10 seconds, measuring the combustion time t1 of the specimen and recording the combustion pattern, ② when the combustion is finished after the first contact, the specimen is contacted again for 10 seconds Measure the combustion time t2 and glowing time t3 of is determined and grades (V-0, V-1, V-2) are calculated.

Hereinafter, the present invention will be described in more detail through specific examples. The scope of the present invention may be variously modified in addition to the examples presented below, and is not limited by the examples.

<Example 1> Step 1 (diethyl (hydroxymethyl) phosphonate) synthesis

As shown in Scheme 3 below and FIGS. 1A to 1C, diethyl phosphite (DEP) represented by Formula 4a and formaldehyde represented by Formula 5 were subjected to a condensation reaction in the presence of a triethylamine catalyst to obtain Formula 2a The indicated diethyl (hydroxymethyl) phosphonate (DEHMP) was synthesized.

3A shows ¹ H-NMR and ³¹ P-NMR spectra of DEHMP.

[Scheme 3]

That is, diethyl phosphite (DEP) was stirred with triethylamine (TEA) in a 3-neck 250 ml flask under a nitrogen atmosphere, and then 35% formaldehyde aqueous solution was slowly added thereto, followed by reaction at 40° C. for 4.5 hours.

After the reaction was completed, diluted with dichloromethane, washed once with distilled water, removed moisture using Na ₂ SO ₄ , and then the solvent was removed using a rotary evaporator, followed by fractional distillation at 120° C. and purified to synthesize diethyl (hydroxymethyl) phosphonate (DEHMP).

<Example 2> Step 2 (bis((diethoxyphosphoryl)methyl)phenylphosphonate) synthesis

As shown in Scheme 4 and Figures 2a to 2e, in the presence of a triethylamine catalyst, diethyl (hydroxymethyl) phosphonate (DEHMP) represented by Formula 2a and phenylphosphonic disulfide represented by Formula 3a Chloride (PPDC) was subjected to a condensation reaction to synthesize bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by Chemical Formula 1a.

3B shows ¹ H-NMR and ³¹ P-NMR spectra of the bis((diethoxyphosphoryl)methyl)phenylphosphonate.

[Scheme 4]

That is, diethyl (hydroxymethyl) phosphonate (DEHMP), TEA, and chloroform were put in a 250 ml three-necked flask and stirred, and then the reactant was cooled to 0 ° C., and then phenylphosphonic dichloride was added to 10 ml of chloroform under a nitrogen atmosphere. After dissolving, it was slowly added over 1 hour while maintaining at 0° C. and reacted for 2 hours.

After removing TEA, the reaction product was washed with distilled water for 5 times and then water was removed using Na ₂ SO ₄ , the solvent was removed using a rotary evaporator, and then vacuum dried at room temperature for 24 hours. Bis((diethoxyphosphoryl)methyl)phenylphosphonate was synthesized.

<Example 3 and Comparative Examples 1-5> Preparation of flame retardant (1)

The bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by Chemical Formula 1a synthesized in Example 2 has a composition as shown in Table 1 (unit: phr) below, which is 5 to 50 phr, at 170° C., 300 A flame retardant composition was prepared under the molding conditions of the second.

At this time, the content of the compound (Formula 1a) of Example 2 and the phosphorus content in the flame retardant are shown in Table 2 below.

<Experimental Example 1> Flame retardant evaluation (1)

The results of evaluation of the flame retardant properties such as hardness and mechanical strength (tensile strength, elongation, tear strength) of the flame retardant compositions prepared in Examples 3 and 1 to 5 are shown in Table 3 below.

At this time, the hardness was measured according to ASTM D2240 standard using a durometer hardness tester, the tensile strength and elongation were measured according to ASTM D638 standard using a universal testing machine, and the tear strength was measured according to ASTM D624 standard did

In addition, the flame-retardant properties were carried out by a vertical flame-retardant test method (UL94 V).

The burner to burn the specimen uses methane gas as a raw material, and generates a calorific value of 37 MJ/m3 and a flame height of 20 mm. The distance between one end of the test specimen and the end of the burner was set to 10 mm, and each specimen was burned twice for 10 seconds each.

The extinguishing time (t1 sec) after the first combustion was measured, and the extinguishing time (t2 sec) after the second combustion was measured. After the second combustion, the flame disappeared, and the duration (t3 seconds) of non-chlorinated combustion (there is no flame, but glowing red like charcoal) was measured. The criteria for judging the V-0, V-2 and V-3 grades for each test specimen were in accordance with Table 4 below.

As shown in Table 3, with the exception of Example 3, Comparative Examples 1 to 5 could not be blended due to a problem of poor compatibility with the base polymer, and migration occurred during sheet molding.

From this, it can be seen that when the compound of Example 2 (Formula 1a) is used alone, the maximum input amount is 5 phr, and it is necessary to mix silica or melamine cyanurate (MC).

<Example 4-5 and Comparative Example 6-8> Preparation of flame retardant (2)

Bis ((diethoxyphosphoryl) methyl) phenylphosphonate represented by Formula 1a synthesized in Example 2 has a composition as shown in Table 5 (unit: phr) below in which 0 to 30 phr, but migration prevention and processability To secure, the compound was impregnated with silica (zeosil 175) and blended to prepare a flame retardant composition under molding conditions of 170° C. and 300 seconds.

At this time, the content of the compound (Formula 1a) of Example 2 and the phosphorus content in the flame retardant are shown in Table 6 below.

<Experimental Example 2> Flame retardant evaluation (2)

The results of evaluation of flame retardant properties such as hardness and mechanical strength (tensile strength, elongation, tear strength) of the flame retardant compositions prepared in Examples 4 to 5 and Comparative Examples 6 to 8 are shown in Table 7 below.

At this time, the hardness, mechanical strength and flame retardant properties were performed in the same manner as in Experimental Example 1.

As shown in Tables 6 and 7, it can be seen that the flame retardancy is excellent when the phosphorus content in the flame retardant is 3% by weight or more.

<Examples 6-7 and Comparative Examples 9-11> Preparation of flame retardant (3)

The bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by Formula 1a synthesized in Example 2 was 0 to 15 phr, and the grade of EPDM was changed to Nordel IP 3722P (Dow Chemical), A flame retardant composition was prepared under the molding conditions of 170 ° C. and 300 seconds by mixing the composition as shown in Table 8 (unit: phr), including the existing flame retardant melamine cyanurate (MC).

At this time, the content of the compound (Formula 1a) of Example 2 and the phosphorus content in the flame retardant are shown in Table 9 below.

<Experimental Example 2> Flame retardant evaluation (2)

The results of evaluation of flame retardant properties such as hardness and mechanical strength (tensile strength, elongation, tear strength) of the flame retardant compositions prepared in Examples 6 to 7 and Comparative Examples 9 to 11 are shown in Table 10 below.

At this time, the hardness, mechanical strength and flame retardant properties were performed in the same manner as in Experimental Example 1.

As shown in Tables 9 and 10, it can be seen that the phosphorus content in the flame retardant when mixed with melamine cyanurate (MC) exhibits V-0 characteristics at 1.2 wt% or more.

In addition, it can be seen that when 10 phr of the compound of Example 2, which is a novel flame retardant component, is used, it exhibits the same flame retardant performance as 10 phr savings of graphite.

On the other hand, it can be seen that when the compound of Example 2, which is a novel flame retardant component, is used for 10 phr or more, the hardness increases and the mechanical strength is improved.

So far, specific examples of the organophosphorus compound according to an embodiment of the present invention, a method for preparing the same, and a flame retardant composition including the same have been described, but various implementation modifications are possible without departing from the scope of the present invention. self-evident

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and their equivalents All changes or modifications derived from the concept should be construed as being included in the scope of the present invention.

Claims (21)

An organophosphorus compound represented by the following formula (1):
[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox period, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group,
R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.
The method of claim 1,
The organophosphorus compound is an organophosphorus compound, characterized in that it is bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by the following formula (1a):
[Formula 1a]

A method for preparing an organophosphorus compound represented by the following formula (1) by condensing a compound represented by the following formula (2) and a compound represented by the following formula (3):
[Formula 1]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox period, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group,
R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.
[Formula 2]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.
[Formula 3]

In the above formula, R ₃ is a C1-C15 alkyl group, a C6-C20 aryl group, a C1-C10 alkyl-substituted C6-C20 aryl group, or a C6-C20 aralkyl group.
4. The method of claim 3,
The compound represented by Formula 2 is a method for preparing an organophosphorus compound, characterized in that it is prepared by condensing a compound represented by Formula 4 and a compound represented by Formula 5:
[Formula 4]

In the above formula, R ₁ and R ₂ are independently hydrogen, C1-C15 alkyl group, C6-C20 aryl group, C7-C15 aralkyl group, C7-C15 alkylaryl group, C1-C15 alkoxy group, C6-C12 arylox group, a C7-C15 aralkyloxy group or a C7-C15 alkylaryloxy group.
[Formula 5]

4. The method of claim 3,
The organophosphorus compound represented by Compound 1 is bis((diethoxyphosphoryl)methyl)phenylphosphonate represented by the following Chemical Formula 1a. Method for preparing an organophosphorus compound:
[Formula 1a]

4. The method of claim 3,
The compound represented by the formula (2) is a method for preparing an organophosphorus compound, characterized in that the diethyl (hydroxymethyl) phosphonate represented by the following formula (2a):
[Formula 2a]

4. The method of claim 3,
The compound represented by Formula 3 is a method for preparing an organophosphorus compound, characterized in that it is phenylphosphonic dichloride represented by Formula 3a:
[Formula 3a]

5. The method of claim 4,
The compound represented by the formula (4) is a method for preparing an organophosphorus compound, characterized in that diethyl phosphite represented by the following formula (4a):
[Formula 4a]

4. The method of claim 3,
A method for producing an organophosphorus compound, characterized in that the compound represented by the formula (2) and the compound represented by the formula (3) are reacted in a molar ratio of 2-3: 1.
10. The method of claim 9,
A method for producing an organophosphorus compound, characterized in that the compound represented by the formula (2) and the compound represented by the formula (3) are reacted in a molar ratio of 2.4: 1.
4. The method of claim 3,
The condensation is selected from the group consisting of water, dichloromethane, C1-C4 anhydrous or hydrous lower alcohol, propylene glycol, butylene glycol, glycerin, acetone, ethyl acetate, chloroform, butyl acetate, diethyl ether, hexane and mixtures thereof. A method for preparing an organophosphorus compound, characterized in that it is carried out under any one solvent.
4. The method of claim 3,
The method for producing an organophosphorus compound, characterized in that the condensation is carried out in the presence of a triethylamine catalyst.
5. The method of claim 4,
A method for producing an organophosphorus compound, characterized in that the compound represented by Formula 4 and the compound represented by Formula 5 are reacted in a molar ratio of 1:1 to 2.
14. The method of claim 13,
A method for producing an organophosphorus compound, characterized in that the compound represented by Formula 4 and the compound represented by Formula 5 are reacted in a molar ratio of 1:1.5.
A flame retardant composition comprising the organophosphorus compound according to claim 1 or 2.
16. The method of claim 15,
The flame retardant composition further comprises at least one selected from the group consisting of ethylene propylene rubber, silica, graphite, and melamine-based flame retardants.
17. The method of claim 16,
The melamine-based flame retardant is a flame retardant composition, characterized in that at least one selected from the group consisting of melamine cyanurate, melamine phosphate, melamine borate and melamine metal phosphate.
16. The method of claim 15,
The phosphorus content in the flame retardant composition is a flame retardant composition, characterized in that 1.2 to 4.3% by weight.
17. The method of claim 16,
Based on 100 parts by weight of the ethylene propylene rubber, 3 to 7 parts by weight of the silica, 10 to 20 parts by weight of the graphite, and 10 to 20 parts by weight of the melamine-based flame retardant.
16. The method of claim 15,
Tensile strength of the flame retardant composition is 10-50 A flame retardant composition, characterized in that kg/cm2.
16. The method of claim 15,
The flame retardant composition is a flame retardant composition, characterized in that it has a flame retardancy of V-0 grade as a result of the UL-94 vertical flame retardant test method.

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