KR101332439B1 - Pentaerythritol diphosphonate, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same - Google Patents

Abstract

(상기에서, R은 C₄-C₁₀의 알킬기, C₆-C₂₀ 아릴기, C₆-C₂₀ 알킬 치환 아릴기, CC₆-C₂₀ 아르알킬기이고, n은 0 또는 1임).The present invention is characterized in that the acid value is improved by post-treatment with alkylene oxide in the process for preparing a phosphorus compound of Formula 1 below:
[Formula 1]

(In the above, R is an alkyl group of C ₄ -C ₁₀ , C ₆ -C ₂₀ An aryl group, a C ₆ -C ₂₀ Alkyl substituted aryl group, CC ₆ -C ₂₀ aralkyl group, n is 0 or 1.

Description

Phosphorus-based compound, preparation method thereof, and flame-retardant thermoplastic resin composition comprising the same

The present invention relates to a phosphorus compound and a flame retardant thermoplastic resin composition comprising the same. More specifically, the present invention relates to a phosphorus-based compound having an acid value improved by post-treatment with an alkylene oxide in the synthesis of the phosphorus-based compound using an acid catalyst and a thermoplastic resin composition to which it is applied as a flame retardant.

In general, polycarbonate resin is excellent in transparency, impact resistance, heat resistance and electrical properties, and is applied to a large injection molding product that emits a lot of heat, such as electrical, electronic and other office equipment. Therefore, it is essential to maintain flame retardancy and high mechanical strength.

A conventional technique for imparting flame retardancy to such a resin composition is to use a phosphate ester flame retardant. However, in order to exhibit the effect of flame retardancy by the addition of phosphate ester, there is a problem in that a predetermined amount or more of a flame retardant or a flame retardant aid is added.

U.S. Patent No. 4,178,281 discloses a flame retardant resin composition which achieves flame retardancy by using pentaerythritol diphosphonate as a flame retardant in a polycarbonate resin.

Such pentaerythritol diphosphonates are usually prepared under acidic catalysts. However, when pentaerythritol diphosphonate is prepared by deoxidation under an acid catalyst, an unreacted hydroxy group exists to increase the acid value. This causes the degradation of the polycarbonate resin during processing has a disadvantage of lowering the physical properties. In addition, if the number of times of washing in the post-treatment process is increased in order to lower the acid value through the removal of the unreacted hydroxyl group, the yield decreases and the manufacturing efficiency decreases.

In order to lower the acid value, it is common to neutralize using Sodium Hydroxide or Potassium Hydroxide during post-treatment. However, in this case, the acid value is lowered, but the sodium or potassium ions remain in the final product. When the mixture is mixed with a thermoplastic resin such as polycarbonate, the thermoplastic resin is decomposed to lower the molecular weight and affect the physical properties. Will result.

Therefore, it is necessary to develop a method for preparing a phosphorus compound having a low acid value without increasing the number of washings or neutralizing alkali.

An object of the present invention is to provide a method for producing a phosphorus compound having a lower acid value.

Another object of the present invention is to provide a method that can significantly reduce the acid value without increasing the number of washing with water, and can produce a phosphorus compound in high yield.

Still another object of the present invention is to provide a method for producing a phosphorus-based compound which does not neutralize with alkali and does not retain alkali metal ions.

Still another object of the present invention is to provide a flame retardant thermoplastic resin composition in which physical properties are not lowered by applying the phosphorus compound prepared above as a flame retardant.

One aspect of the invention relates to a process for the preparation of phosphorus compounds. The method comprises reacting pentaerythritol with phosphonic dichloride under an acid catalyst; And treating the reaction product with alkylene oxide.

The alkylene oxide may be represented by the following formula (2):

(2)

(Wherein R ₂ is hydrogen, a C ₁ -C ₆ alkyl group, a C ₆ -C ₂₀ An aryl group, a C ₆ -C ₂₀ Substituted alkylaryl group, C ₆ -C ₂₀ Lt; / RTI >

In embodiments, the pentaerythritol and phosphonic dichloride may be refluxed with 2 to 4 equivalents of phosphonic dichloride relative to 1 equivalent of pentaerythritol.

In embodiments, the alkylene oxide may be added in 2 to 6 equivalents of the acid value of the reaction product.

In one embodiment, the reaction product may be reacted to reflux with alkylene oxide after removing moisture.

Another aspect of the present invention relates to a phosphorus compound prepared by the above method. The phosphorus compound has an acid value of 0.1 mg KOH / g or less and is characterized by not containing alkali metal ions.

Another aspect of the present invention relates to a flame retardant thermoplastic resin composition containing the phosphorus compound.

In one embodiment, the thermoplastic resin composition may include 0.1 to 30 parts by weight of the phosphorus compound based on 100 parts by weight of the polycarbonate resin.

In an embodiment, the flame retardant thermoplastic resin composition may have a number average molecular weight of 10,000 to 20,000 g / mol and a weight average molecular weight of 25,000 to 40,000 g / mol.

The present invention provides a phosphorus compound and a method for producing the phosphorus compound which can significantly reduce the acid value without increasing the number of washing, can produce a phosphorus compound in a high yield, and does not neutralize with alkali so that no alkyl metal ions remain. The phosphorus-based compound prepared above is applied as a flame retardant to provide a flame retardant thermoplastic resin composition in which physical properties are not lowered.

The present invention provides a method for preparing a phosphorus compound represented by the following formula (1).

[Formula 1]

(In the above, R is an alkyl group of C ₄ -C ₁₀ , C ₆ -C ₂₀ An aryl group, a C ₆ -C ₂₀ Alkyl-substituted aryl group, CC ₆ -C ₂₀ Aralkyl group, n is 0 or 1).

The method comprises reacting pentaerythritol with phosphonic dichloride under an acid catalyst; And treating the reaction product with alkylene oxide.

The phosphonic dichloride may be represented by the following formula 3:

(3)

(Wherein R is a C ₄ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ alkyl substituted aryl group, a C ₆ -C ₂₀ aralkyl group).

The alkyl substituted aryl group is a C ₆ -C ₂₀ aryl group substituted with a C ₁ -C ₁₀ alkyl group.

The reaction of the pentaerythritol with phosphonic dichloride can be carried out by a conventional method under an acid catalyst.

In an embodiment, the acid catalyst may be preferably applied with a Lewis acid catalyst. For example, AlCl ₃ , BF ₃ , FeCl ₃ , TiCl ₄ , ZnCl ₂ , MgCl _2, etc. may be used, but is not necessarily limited thereto.

Preferably, the pentaerythritol and phosphonic dichloride may be refluxed with 2 to 4 equivalents of phosphonic dichloride relative to 1 equivalent of pentaerythritol.

In one embodiment, the reaction may be terminated and washed with an acid solution. The acid solution may be applied phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, preferably phosphoric acid or hydrochloric acid. At this time, the acid solution is preferably 0.1 to 10%, preferably 1 to 5% concentration.

The reaction product washed with the acid solution is reacted with an alkylene oxide represented by the following formula (2). In a specific embodiment, the reaction may be stably progressed by removing water through a dehydration process before reacting with the alkylene oxide.

(2)

(Wherein R ₂ is hydrogen, a C ₁ -C ₆ alkyl group, a C ₆ -C ₂₀ An aryl group, a C ₆ -C ₂₀ Substituted alkylaryl group, C ₆ -C ₂₀ Lt; / RTI >

Wherein R ₂ in the preferred embodiment may be an alkyl group of C ₁ -C _6.

In an embodiment, the alkylene oxide may be added in 2-6 equivalents, preferably 3-5 equivalents, of the acid value of the reaction product. The reaction efficiency is excellent in the above range.

The reaction between the reaction product and the alkylene oxide is performed for about 0.1 to 5 hours. The reaction temperature may be 20 to 150 ° C, preferably 110 to 140 ° C. In this range, the reaction can proceed effectively.

After the reaction between the reaction product and the alkylene oxide, washing and filtration may be further performed.

The phosphorus-based compound prepared as described above does not contain alkali ions because the acid value is 0.1 mg KOH / g or less and does not neutralize with an alkaline solution.

Therefore, the phosphorus-based compound does not cause decomposition of the thermoplastic resin to be mixed because hardly any unreacted hydroxyl group remains, and can be preferably applied as a flame retardant.

Another aspect of the present invention relates to a flame retardant thermoplastic resin composition containing the phosphorus compound.

The kind of the thermoplastic resin is not particularly limited. For example, a styrene resin, a polyamide, a polycarbonate, a polyester, a polyvinyl chloride, a styrenic copolymer resin, a (meth) acrylic resin, a polyphenylene ether resin, and the like can be applied.

Phosphorus-based compounds produced by the process of the present invention are particularly suitable for polycarbonate resins that are vulnerable to unreacted hydroxyl groups because they have a low acid value and do not contain alkali metal ions.

In one embodiment, the flame retardant thermoplastic resin composition may include 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight of the phosphorus compound, based on 100 parts by weight of the polycarbonate resin.

In a specific embodiment, since the flame retardant thermoplastic resin composition does not cause decomposition of the polycarbonate by an unreacted hydroxyl group of the phosphorus compound, the number average molecular weight may be 10-20 g / mol and the weight average molecular weight may be 25-40 g / mol.

Hereinafter, the present invention will be described in more detail with reference to Examples, which should be construed as illustrative of the present invention but not limited to the scope of the present invention.

Example

Example  One: Diphenyl Pentaerythritol Diphosphonate  Produce

1 equivalent of pentaerythritol (manufactured by Perstorp), 2 equivalents of phenyl phosphonic dichloride (manufactured by Aldrich) and 0.1 equivalents of magnesium chloride (manufactured by samchun) were added to 1,2-Dichloroethane (manufactured by Aldrich), followed by reflux reaction. After completion of the reaction, the water layer was removed after washing with a 10% concentration of phosphate solution, and the water was completely removed by proceeding with a dehydration reaction at 130 degrees. After taking some samples, the acid value was measured, and 5 equivalents of propylene oxide (manufactured by Aldrich) of the acid value was added and refluxed for 2 hours. Thereafter, water was added thereto, washed twice, and then filtered to obtain diphenyl pentaerythritol diphosphonate.

Example  2 : Dianisol Pentaerythritol Diphosphonate  Produce

The same procedure as in Example 1 was carried out except that anisole phosphonic dichloride (manufactured by IDB Chem.) Was used instead of phenyl phosphonic dichloride.

Example  3: Ditoryl Pentaerythritol Diphosphonate  Produce

The same procedure as in Example 1 was carried out except that tolyl phosphonic dichloride was used instead of phenyl phosphonic dichloride.

Comparative Example  One

1 equivalent of pentaerythritol, 2 equivalents of phenyl phosphonic dichloride, and 0.1 equivalent of magnesium chloride were added to 1,2-Dichloroethane and refluxed. After completion of the reaction, washed with 10% concentration of phosphoric acid solution, water was added, washed twice and filtered to obtain diphenyl pentaerythritol diphosphonate.

Comparative Example  2 : Dianisol Pentaerythritol Diphosphonate  Produce

The same procedure as in Comparative Example 1 was carried out except that anisole phosphonic dichloride was used instead of phenyl phosphonic dichloride.

Comparative Example  3: Ditoryl Pentaerythritol Diphosphonate  Produce

The same procedure as in Comparative Example 1 was carried out except that tolyl phosphonic dichloride was used instead of phenyl phosphonic dichloride.

The pentaerythritol diphosphonate prepared in Examples 1 to 3 and Comparative Example 3 was measured in the acid value and yield by the following method and shown in Table 1.

Acid value (mg KOH / g): 1 ~ 20g of the sample was dissolved in dimethyl sulfoxide (50ml) and a small amount of BTB solution was added, titrated with 0.1N NaOH solution and measured.

Acid value = ((0.1N NaOH solution consumption ml) * (0.1N NaOH solution Factor) * 5.61) / sample amount (g)

Alkylene oxide
Applicability Washings Mountain Yield Example 1 O 2 0.1 90% Example 2 O 2 0.1 81% Example 3 O 2 0.1 80% Comparative Example 1 X 2 36.4 50% Comparative Example 2 X 2 33.5 68% Comparative Example 3 X 2 35.4 61%

As shown in Table 1, in Examples 1 to 3 to which the method of the present invention was applied, the acid value was significantly lower than that of Comparative Examples 1 to 3, and it can be seen that pentaerythritol diphosphonate can be produced in high yield. .

Manufacture of thermoplastic resin composition

Example 4

Diphenyl pentaerythritol diphosphonate prepared in Example 1 was added to the polycarbonate, and the pellets were prepared by extrusion at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder. After dissolving the pellet in 0.01 g to 0.015 g in 2 mL of MC, about 10 mL of THF was diluted and the dissolved sample was filtered using a 0.45 μm syringe filter to measure the molecular weight by gel permeation chromatography (GPC). UL 94 VB Flame retardancy was measured at 1/8 "thickness in accordance with flame retardancy regulations.

Comparative Example 4

Except for using the diphenyl pentaerythritol diphosphonate prepared in Example 1 instead of the diphenyl pentaerythritol diphosphonate prepared in Example 1 was carried out in the same manner as in Example 4.

Comparative Example 5

The same procedure as in Example 4 was carried out except that phosphate ester (PX-200 available from Daihachi Co., Ltd.) was used instead of diphenylpentaerythritol diphosphonate.

Comparative Example 6

The same procedure as in Example 4 was carried out except that diphenylpentaerythritol diphosphonate was not added.

Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polycarbonate 100 100 100 100 Diphenylpentaerythritol diphosphonate (acid value = 0.1) 5 - - - Diphenylpentaerythritol diphosphonate (acid value = 36.4) - 5 - - Phosphate Ester - - 5 - Number average molecular weight (kg / mol) 13.8 9.4 14.1 16.6 Mass average molecular weight (kg / mol) 27.1 19.7 27.5 29.8 Flammability V-0 V-2 V-1 FAIL Impact Strength (1/8 ") 8.8 2.3 6.1 80.5

As shown in Table 2, when the pentaerythritol diphosphonate prepared by the method of the present invention is applied, there is little decomposition of the polycarbonate, and it can be seen that it has excellent flame retardancy even with a small content.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (10)

In the method for preparing a phosphorus compound represented by the following formula (1) as a reaction product by reacting pentaerythritol and phosphonic dichloride under an acid catalyst,
Treating the reaction product with an alkylene oxide;
≪ / RTI >
The alkylene oxide is a method of producing a phosphorus compound represented by the following formula (1), characterized in that the addition of 2 to 6 equivalents of the acid value of the reaction product:
[Formula 1]

(Wherein R is a C ₄ -C ₁₀ alkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ alkyl substituted aryl group, CC ₆ -C ₂₀ aralkyl group, n is 0 or 1).

The method of claim 1, wherein the alkylene oxide is represented by the following formula (2):
(2)

(Wherein R ₂ is hydrogen, a C ₁ -C ₆ alkyl group, a C ₆ -C ₂₀ An aryl group, a C ₆ -C ₂₀ Substituted alkylaryl group, C ₆ -C ₂₀ Lt; / RTI >
The method of claim 1, wherein the pentaerythritol and the phosphonic dichloride are reacted with 2 to 4 equivalents of phosphonic dichloride relative to 1 equivalent of pentaerythritol.
The method of claim 1 wherein the reaction product is washed with an acid solution prior to treatment with alkylene oxide.
The method of claim 1 wherein the reaction product is refluxed with alkylene oxide after removing moisture.
The method of claim 1 wherein the method does not neutralize with alkaline solution.
A phosphorus compound prepared by the method of any one of claims 1 to 5, having an acid value of 0.1 mg KOH / g or less and containing no alkali metal ions.
A flame retardant thermoplastic resin composition comprising the phosphorous compound of claim 7.
The flame retardant thermoplastic resin composition of claim 8, wherein the composition comprises 0.1 to 30 parts by weight of the phosphorus compound based on 100 parts by weight of the polycarbonate resin.
The flame retardant thermoplastic resin composition of claim 9, wherein the flame retardant thermoplastic resin composition has a number average molecular weight of 10,000 to 20,000 g / mol and a weight average molecular weight of 25,000 to 40,000 g / mol.