KR101004674B1 - Symmetric Cyclic Phosphonate Compound, Method of Preparing the Same and Flame Retardant Styrenic Resin Composition Comprising the Same - Google Patents

Abstract

The present invention provides a symmetric cyclic phosphate compound represented by the following formula (1), a method for preparing the same, and a flame retardant styrene resin composition including the same. The styrene resin composition to which the symmetric cyclic phosphorus compound represented by the following Chemical Formula 1 is applied is excellent in flame retardancy, does not generate halogenated gas during processing or combustion, and is environmentally friendly, and has excellent impact strength.

[Formula 1]

In Formula _1, R 1 and R ₂ is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ independently from each other.

Symmetric cyclic phosphorus compounds, styrene resins, polyphenylene ether resins

Description

Symmetric Cyclic Phosphonate Compound, Method of Preparing the Same and Flame Retardant Styrenic Resin Composition Comprising the Same}

1 shows the results of GC-MS analysis of the symmetric cyclic phosphorus-based compound (I-1) prepared in Example 1 of the present invention.

Figure 2 shows the results of the ¹ H-NMR analysis of the symmetric cyclic phosphate compound (I-1) prepared in Example 1 of the present invention.

3 shows the results of PNMR analysis of the symmetric cyclic phosphorus compound (I-1) prepared in Example 1 of the present invention.

Field of invention

The present invention relates to a novel phosphorus compound and a flame retardant styrene resin composition comprising the same. More specifically, the present invention relates to a symmetric cyclic phosphorus compound having a novel structure and a styrene resin composition having excellent flame retardancy by applying it as a flame retardant to a blend resin using a styrene resin and a polyphenylene ether resin.

Background of the Invention

Styrene-based resins are generally applied to almost all electronic products as exterior materials of electronic products due to their excellent processability and mechanical properties. However, since combustion can easily occur due to its own characteristics of styrene resin, it is pointed out as a problem that there is no resistance to fire. In particular, since the styrene resin can easily be burned by an external ignition source, it is a bigger problem that it can play a role of further spreading the fire when a fire occurs. In particular, in the United States, Japan, and Europe, styrene-based resins are flame-retardant considering that the law regulates that only polymer resin satisfying the flame retardant specification is used as an exterior material in order to ensure the safety of fire of electronic products. Is a very necessary technique to broaden its application.

The most widely known flame retardant method of styrene resin is to use a halogen-based compound as the main flame retardant to rubber-reinforced styrene resin and to apply the antimony-based compound as a flame retardant to impart flame retardancy. Halogen compounds used herein include polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds and chlorinated polyethylene, and antimony compounds include antimony trioxide and antimony pentoxide.

In case of imparting flame retardancy by using halogen-based and antimony-based compounds, it is easy to secure flame retardancy and hardly deteriorate in physical properties. Therefore, main materials such as housing materials of electrical or office equipment, ABS resin, PS, PBT, PET, epoxy resin, etc. It is used as a flame retardant. However, the hydrogen halide gas generated during processing may have a fatal effect on the human body, and due to its natural decomposition, it has high environmental residual property and does not dissolve well in water, thereby increasing bioaccumulation. In particular, since the highly toxic gases such as dioxins and furans are generated during the combustion of polybromodiphenyl ethers, which are mainly halogen-based flame retardants, they have a critical weakness that they are not friendly or environmentally friendly. Therefore, many efforts have been made to develop flame retardant methods that do not apply halogen-based compounds.

Accordingly, the present inventors have developed a symmetric cyclic phosphonate and applied it to a styrene resin, thereby developing a styrene resin composition excellent in flame retardancy.

An object of the present invention is to provide a novel symmetrical cyclic phosphorus-based compound capable of expressing excellent flame retardancy and a method for producing the same.

Another object of the present invention to provide an environmentally friendly flame retardant resin composition using the symmetric cyclic phosphorus compound as a flame retardant.

Another object of the present invention is to provide an environment-friendly flame-retardant resin composition excellent in impact resistance and moldability by using the symmetric cyclic phosphorus compound as a flame retardant, and also by reducing the amount of polyphenylene ether added.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

The novel symmetric cyclic phosphorus compounds of the present invention are represented by the following formula (1).

[Formula 1]

In Formula _1, R 1 and R ₂ is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ independently from each other.

Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

Symmetric Cyclic Phosphorus Compound

Symmetrical cyclic phosphorus compounds according to the present invention are represented by the following formula (1).

[Formula 1]

In Formula _1, R 1 and R ₂ is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ independently from each other.

In Formula 1, R ₁ and R ₂ is more preferably an alkyl group of C _{1 ~} C ₆ independently of each other. For example, R ₁ and R ₂ may be independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and isoamyl groups. Can be.

Specific examples of the phosphorus compound represented by Formula 1 include a compound represented by Formula 1-1.

[Formula 1-1]

In Formula 1-1, Et is an ethyl group and t-Bu is a tert-butyl group.

Method for preparing symmetric cyclic phosphorus compound

The present invention provides a method for synthesizing the symmetric cyclic phosphorus compound. The symmetric cyclic phosphate compound may be prepared by reacting a phosphonic dichloride represented by the following Formula 2 with a polyol represented by the following Formula 3 under a base.

In the specific example of this invention, it is preferable to carry out reflux reaction of the phosphonic dichloride represented by following formula (2) and the polyol represented by following formula (3).

[Formula 2]

In Formula _2, R 2 is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ a.

(3)

In Formula 3, R ₁ is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ a.

Specifically, 1 equivalent ratio of the polyol represented by Formula 3 is applied to 2 equivalent ratios of phosphonic dichloride represented by Formula 2, and the reaction temperature is 80 to 200 ° C., preferably 100 to 150 ° C., under a base and a solvent. The reaction is refluxed for 5 to 20 hours, preferably 7 to 15 hours.

It is preferable to use the said base in 4 equivalent ratio or more. The compound which can be used as the base is not particularly limited, and for example, triethylamine, pyridine, sodium hydroxide and the like can be used. As the solvent, a conventional organic solvent can be used without limitation. For example, toluene, benzene, xylene, 1,4-dioxane, methylene chloride and the like can be used.

Since the symmetric cyclic phosphorus-based compound of the present invention exhibits structural symmetry, when used as a flame retardant due to its high phosphorus content, it may exhibit excellent flame retardancy. In addition, it is eco-friendly because it does not emit halogenated gas.

Flame retardant styrene resin composition

The present invention provides a flame retardant resin composition in which the symmetric cyclic phosphorus compound is applied as a flame retardant.

In one embodiment of the present invention, there is provided a non-halogen flame retardant styrene resin composition wherein the symmetric cyclic phosphorus compound is applied to a styrene resin.

The non-halogen flame-retardant styrene resin composition is 100 parts by weight of a base resin consisting of (A) a styrene resin and (B) a polyphenylene ether resin, and (C) a symmetric cyclic phosphorus compound represented by the formula (1) or a mixture thereof 0.5 It comprises -50 parts by weight. Hereinafter, each component is explained in full detail.

(A) styrene resin

The styrene resin (A) which can be used in the resin composition of the present invention is, for example, polystyrene resin, rubber modified aromatic vinyl-vinyl cyanide graft copolymer resin, rubber modified high impact polystyrene resin (HIPS), and the like. no.

The styrene resin (A) is preferably prepared by further adding an alkyl ester monomer, an unsaturated nitrile monomer or a mixture thereof to the rubber and the aromatic monoalkenyl monomer.

The styrene-based resin (A) is usually polymerized in the presence of an initiator, but can be polymerized by thermal polymerization without the presence of an initiator. As the polymerization initiator, at least one of peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, and azo initiators such as azobis isobutyronitrile may be selected and used. However, it is not necessarily limited thereto.

As the polymerization method of the styrene-based resin (A), a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof is used, and among these methods, a bulk polymerization method is preferably used.

The rubber used in the polymerization of the styrene resin (A) is selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrenes, alkyl acrylate rubbers and the like, and the total of the styrene resins (A) It is preferably 3 to 30% by weight, more preferably 5 to 15% by weight based on the weight.

The monomer used in the polymerization of the styrene resin (A) is an aromatic monoalkenyl monomer, preferably 70 to 97% by weight, more preferably 85 to 90% by weight based on the total weight of the styrene resin (A). Use In addition, by adding and polymerizing monomers such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide to the aromatic monoalkenyl monomer, properties such as chemical resistance, processability and heat resistance can be imparted. The amount added at this time is preferably 40 parts by weight or less based on 100 parts by weight of the total of monomers.

In order to achieve optimum physical properties of the styrene-based resin (A) in the blend with the polyphenylene ether resin (B), the rubber particle size is preferably 0.1 to 4.0 µm.

The styrene-based resin (A) is used in 60 to 99% by weight, preferably 65 to 90% by weight, more preferably 70 to 85% by weight based on the total weight of the base resin (A) + (B). do.

(B) polyphenylene ether resin

The resin composition according to the present invention is used as a component of the base resin by adding a polyphenylene ether resin (B) in order to overcome the insufficient flame resistance and heat resistance of the styrene resin (A). Such polyphenylene ether resins (B) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6) -Dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether , Poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4- Copolymer of phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3) And copolymers of, 5-triethyl-1,4-phenylene) ether, but are not necessarily limited thereto. These may be used alone or in mixture of two or more thereof. Preferably a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl -1,4-phenylene) ether is used, of which poly (2,6-dimethyl-1,4-phenylene) ether is most preferred.

Although the degree of polymerization of the polyphenylene ether resin (B) used in the present invention is not particularly limited, the intrinsic viscosity measured in a chloroform solvent at 25 ° C. in consideration of the thermal stability and workability of the resin composition is preferably 0.2 to 0.8. Do.

In the present invention, the polyphenylene ether resin (B) is used in an amount of 1 to 40% by weight, preferably 10 to 35% by weight, more preferably 15 to 15, based on the total weight of the base resin (A) + (B). Used at 30% by weight. If the polyphenylene ether resin (B) is used in excess of 40% by weight, the moldability is lowered, and when used in less than 1% by weight, the flame retardancy is significantly decreased.

(C) Symmetric cyclic phosphorus compound

The symmetric cyclic phosphorus-based compound used in the resin composition of the present invention is a compound represented by the formula (1) or a mixture thereof.

[Formula 1]

In Formula _1, R 1 and R ₂ is an aryl group of hydrogen, C ₁ ~C ₆ alkyl group or a C ₆ ~C ₂₀ independently from each other.

The symmetric cyclic phosphorus compound (C) represented by the formula (1) is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 2.5 to 35 parts by weight based on 100 parts by weight of the base resin (A) + (B). Used in parts by weight. If the symmetric cyclic phosphorus-based compound (C) is used in an amount exceeding 50 parts by weight, the physical properties such as mechanical strength are lowered, and when used in less than 0.5 part by weight, the flame retardancy tends to be lowered.

In one embodiment of the present invention, the resin composition may further include (D) an aromatic phosphate ester compound, (E) phosphate compound or a mixture thereof in order to have an improved flame retardant effect.

The aromatic phosphate ester compound (D), phosphate compound (E) or a mixture thereof is preferably used in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the base resin (A) + (B), and 5 to 30 parts by weight. More preferably, 10-25 weight part is still more preferable. When the aromatic phosphate ester compound (D), the phosphate compound (E) or a mixture thereof is used in an amount less than 0.1 part by weight, it is difficult to obtain an improved flame retardant effect, and when used in an amount exceeding 40 parts by weight, mechanical properties such as mechanical strength are inferior. .

When using the said aromatic phosphate ester compound (D) and a phosphate compound (E) together, the said aromatic phosphate ester compound (D) is 0.05-30 weight part with respect to 100 weight part of said base resins (A) + (B). It is preferable to use the said phosphate compound (E) at 0.05-10 weight part.

Hereinafter, an aromatic phosphate ester compound (D) and a phosphate compound (E) are explained in full detail.

(D) Aromatic Phosphate Ester Compounds

The aromatic phosphate ester compound used in the present invention has a structure represented by the following general formula (4).

[Formula 4]

In Chemical Formula 4, R ₃ , R _4, and R ₅ are each independently hydrogen or an alkyl group of C _{1 to} C ₄ , and X is a C ₆ to C ₂₀ aryl group or a C ₆ to C ₂₀ aryl substituted with an alkyl group. As group, it is derived from resorcinol, hydroquinol or bisphenol-A. In addition, n is an integer of 0-4.

Examples of the compound corresponding to Chemical Formula 4 when n is 0 include triphenyl phosphate, tri (2,6-dimethyl) phosphate, and the like, but are not necessarily limited thereto. When n is 1, resorcinol bis (diphenyl) phosphate, resorcinol bis (2,6-dimethylphenyl) phosphate, resorcinol bis (2,4-di-butylphenyl) phosphate, hydroquinol bis ( 2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-di-butylphenyl) phosphate, and the like, but are not necessarily limited thereto. These aromatic phosphoric acid ester compounds (D) may be applied alone or may be applied to each mixture.

(E) phosphate compounds

The phosphate compound used in the present invention is an alkyl phosphinic acid metal salt compound having a structure represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, R ₁ and R ₂ are independently hydrogen or an alkyl group of C _{1 to} C ₄ , M is selected from Al, Mg, K, Zn and Ca, which are metals, and n is an integer of 1 to 3. .

Specific examples of the phosphate compound (E) include diethyl phosphinic acid aluminum salt, but are not necessarily limited thereto.

In another embodiment of the present invention, the resin composition may further include various additives depending on the use, in addition to the above-described components. Specific examples of the additives include, but are not limited to, heat stabilizers, anti drip agents, antioxidants, compatibilizers, light stabilizers, plasticizers, pigments, dyes, inorganic additives, and the like. Specific examples of the inorganic additives include glass fibers, asbestos, talc, ceramics, sulfates, and the like, but are not necessarily limited thereto. The additives may be applied alone or in mixture of two or more. The additive is preferably used in an amount of 30 parts by weight or less based on 100 parts by weight of the base resin (A) + (B), and more preferably in an amount of 0.001 to 30 parts by weight.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the above-described components and additives may be mixed together, and then melt-extruded in an extruder to prepare pellets.

The resin composition according to the present invention is excellent in flame retardancy and impact strength and can be applied to various products. In particular, it can be widely used in electrical and electronic products such as TV, computer, audio, air conditioner, office automation, etc. to which strict flame retardant standards are applied.

The invention will be better understood by the following examples. The following examples are for illustrative purposes of the present invention and are not intended to limit or limit the scope of the present invention.

Example

Example 1 Preparation of Symmetric Cyclic Phosphorus Compound

2 equivalent ratios of t-butyl phosphonic dichloride (IV), 1 equivalent ratio of tetraol (V), and 4 equivalents of triethylamine were refluxed at 130 ° C. for 10 hours in a toluene solvent. After the completion of the reaction, water was added, stirred until the solid disappeared, the organic layer was taken, and distilled under reduced pressure to obtain a symmetric cyclic phosphorus compound (I-1) having a purity of 99% or more and a yield of 50%.

(t-Bu: tertiary butyl group (t-butyl), Et: ethyl group (ethyl))

The symmetric cyclic phosphorus compound (I-1) prepared above was subjected to GC-MS analysis, ¹ H-NMR analysis and PNMR analysis, and the analysis results are shown in FIGS. 1, 2, and 3, respectively.

Preparation of flame retardant styrene resin composition

The specification of each component used in the following Examples and Comparative Examples is as follows.

(A) styrene resin

Cheil Industries Ltd. rubber-reinforced styrene resin HG-1760S was used.

(B) polyphenylene ether (PPE) resin

Poly (2,6-dimethyl-1,4-phenylene) ether (trade name: PX-100F) manufactured by Mitsubishi Engineering Plastics, Japan, was used, and the particle size was in the form of a powder having an average particle diameter of several tens of micrometers.

(C) Symmetric cyclic phosphorus compound

The symmetric cyclic phosphorus compound (I-1) prepared in Example 1 was used.

(D) Aromatic Phosphate Ester Compounds

Bisphenol A bis (diphenyl) phosphate (trade name: CR741S) manufactured by Nippon Shofar Chemical Co., Ltd. was used.

(E) phosphate compounds

Clariant's diethyl phosphonic acid aluminum salt (trade name: Exolit OP930) was used.

Examples 2-7

Each component was mixed to the content shown in Table 1, and then extruded at a temperature range of 200 ~ 280 ℃ in a conventional twin screw extruder to produce a pellet. The prepared pellets were dried at 80 ° C. for 2 hours, and then the specimens were prepared by injecting at a mold temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. in a 60 Oz injection machine.

The prepared specimens were measured for flame retardancy at a thickness of 1/8 "according to the UL 94 VB flame retardant standard. Impact strength was measured according to ASTM D 256 (1/8", kg · cm / cm). The measurement results are shown in Table 1 below.

Comparative Examples 1 and 2

As shown in Table 1, except that the content of each component was adjusted, the specimens were prepared in the same manner as in Examples 2 to 7, and physical properties thereof were measured. The measurement results are shown in Table 1 below.

From the results of Table 1, Examples 2 to 7 prepared by using the symmetric cyclic phosphorus compound of the present invention as a flame retardant are Comparative Example 1 and an aromatic phosphate ester compound prepared by using an aromatic phosphate ester compound and a phosphate compound together. It can be seen that the flame retardancy and impact strength is excellent at a thickness of 1/8 "compared to Comparative Example 2 prepared by using alone.

Since the symmetric cyclic phosphorus-based compound of the present invention has a symmetrical structure, it can exhibit excellent flame retardancy due to high phosphorus content. Moreover, it does not discharge halogenated gas and is environmentally friendly.

In addition, the styrene resin composition of the present invention includes the symmetric cyclic phosphorus compound, which is excellent in flame retardancy and environmentally friendly, and has excellent mechanical properties such as impact strength.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

A symmetric cyclic phosphorus compound represented by Formula 1 below: [Formula 1]

In Formula 1, R ₁ and R ₂ are independently hydrogen, an alkyl group of C _{1 ~} C ₆ . A method of synthesizing a symmetric cyclic phosphorus compound of Formula 1 by reacting a phosphonic dichloride represented by Formula 2 with a polyol represented by Formula 3 under a base: [Formula 2]

In Chemical Formula 2, R ₂ is hydrogen, an alkyl group of C _{1 to} C ₆ ; (3)

In Chemical Formula 3, R ₁ is hydrogen, an alkyl group of C _{1 to} C ₆ ; [Formula 1]

In Formula 1, R ₁ and R ₂ are independently hydrogen, an alkyl group of C _{1 ~} C ₆ . 100 parts by weight of a basic resin comprising (A) a styrene resin and (B) a polyphenylene ether resin; And (C) 0.5 to 50 parts by weight of a symmetric cyclic phosphorus compound represented by the following formula (1) or a mixture thereof; Flame retardant styrene resin composition comprising: [Formula 1]

In Formula 1, R ₁ and R ₂ are independently hydrogen, an alkyl group of C _{1 ~} C ₆ . The flame retardant styrene resin composition according to claim 3, wherein the base resin comprises 60 to 99 wt% of styrene resin (A) and 1 to 40 wt% of polyphenylene ether resin (B). The method according to claim 3, further comprising 0.1 to 40 parts by weight of (D) an aromatic phosphate ester compound, (E) a phosphate compound or a mixture thereof based on 100 parts by weight of the base resin (A) + (B). Flame retardant styrene resin composition. The flame-retardant styrene resin composition of claim 5, wherein the aromatic phosphate ester compound (D) has a structure represented by the following general formula (4): [Formula 4]

In Chemical Formula 4, R ₃ , R _4, and R ₅ are each independently hydrogen or an alkyl group of C _{1 to} C ₄ , and X is a C ₆ to C ₂₀ aryl group or a C ₆ to C ₂₀ aryl substituted with an alkyl group. As group, it is derived from resorcinol, hydroquinol or bisphenol-A, n is an integer of 0-4. The flame retardant styrene resin composition according to claim 5, wherein the phosphate compound (E) has a structure represented by the following Chemical Formula 5: [Chemical Formula 5]

In Formula 5, R ₁ and R ₂ are each independently hydrogen or an alkyl group of C _{1 ~} C ₄ , M is selected from Al, Mg, K, Zn and Ca which is a metal, n is an integer of 1-3. The method according to claim 3, wherein, based on 100 parts by weight of the base resin (A) + (B), a heat stabilizer, an antidropping agent, an antioxidant, a compatibilizer, a light stabilizer, a plasticizer, a pigment, a dye, an inorganic additive, and a mixture thereof A flame retardant styrene resin composition further comprising 30 parts by weight or less of an additive selected from the group.

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