JPH0952977A - Phosphoric ester, flame retarder and flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphoric ester as a flame retardant which has good compatibility with resins and can impart resins with flame retardancy without reduction in their transparency and physical properties by adding this ester to a resin such as a polystyrene resin, an ABS resin, a polycarbonate resin and the like. SOLUTION: This phosphoric ester is represented by formula I [R1 is a diol residue containing an aromatic ring in the main chain; at least one of X1 -X4 is a group of formula II (R2 is a 1-6C unsubstituted alkyl, a halogen-substituted alkyl, a halogen, H; (m) is 0-2), and the others of X1 -X4 are groups of formula III (R3 is same as R2 )], e.g. 2,2-bis(4-(phenoxy-4-(α-phenylethyl)phenoxy- phosphinyloxy)phenyl)propane. The compound of formula I is obtained by allowing a divalent diol containing aromatic rings in the main chain to react with a phosphorus oxyhalide to give an intermediate followed by reaction of this intermediate with a specific (substituted) styrene phenol and a specific phenol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phosphoric acid ester compound useful as a flame retardant imparting agent, a flame retardant imparting agent for a synthetic resin, and a flame retardant resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, polystyrene resin, ABS resin,
The following flame retardants have been used as flame retardants for polycarbonate resins, polyphenylene ether resins or blended resins thereof. For example, triphenyl phosphate, tricresyl phosphate, bis (1,3-) described in JP-A-62-280255.
Compounds such as phenylenediphenyl) phosphate, JP-A-5-262933 and JP-A-4-2279
Compounds such as triaryl phosphate, trialkyl phosphate, and alkyl aryl phosphate described in JP-A-54-54, for example, the following chemical formula (4) described in JP-A-6-228426.
And the like.

[0003]

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[0004]

However, the above-mentioned flame retardancy-imparting agent for synthetic resin has insufficient compatibility with the aromatic-containing synthetic resin, so that the transparency of the resin is deteriorated and the physical properties of the resin are deteriorated. There was a problem such as a drop. Further, in the case of triphenyl phosphate, tricresyl phosphate and the like having a relatively small molecular weight, there is a drawback that the flame retardant imparting agent exudes from the resin with the lapse of time and the flame retardancy decreases with the passage of time.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, found that the compatibility was good,
The present inventors have found an excellent flame retardant imparting agent which does not cause deterioration in resin properties, and have reached the present invention.

That is, the first aspect of the present invention is the general formula (1)

[0007]

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[Wherein, R1 is a residue of a diol containing an aromatic ring in the main chain; at least one of X1 to X4 has the following chemical formula (2):

[0009]

[Chemical 6]

A residue of a (substituted) styrenated phenol having a structure represented by the following formula: wherein R2 is an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom. Either of them may be the same or different; m is a number from 0 to 2), and other X1 to X4 are represented by the following chemical formula (3).

[0011]

[Chemical 7]

A (substituted) phenyl group having a structure represented by the formula (wherein R3 is an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom, They may be the same or different.)].

A second aspect of the present invention is a flame retardant-imparting agent (B) for synthetic resin, which comprises a phosphoric acid ester compound (A) as an essential component.

The third aspect of the present invention is to provide a flame retardancy-imparting agent (B),
A flame-retardant resin composition (C) comprising one or more resins selected from the group consisting of polystyrene resin, ABS resin, polycarbonate resin and polyphenylene ether resin.

The phosphoric acid ester compound (A) of the present invention will be described in more detail. In the general formula (1), R
1 is a residue of a diol containing an aromatic ring in the main chain. As the diol containing an aromatic ring in the main chain,
Bisphenols, hydroquinones, biphenols, hydroxyphenylalkyl alcohols; and alkylene oxide adducts thereof, specifically, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) , Bis (4-hydroxyphenyl) methane (hereinafter referred to as bisphenol F
Bis (4-hydroxyphenyl) sulfone (hereinafter referred to as bisphenol S), hydroquinone, 2,2'-dihydroxybiphenyl, 4,4'-hydroxybiphenyl, p-hydroxyphenylethyl alcohol; bisphenol A-ethylene Oxide 2 mol adduct, bisphenol F-ethylene oxide 2 mol adduct, bisphenol S-ethylene oxide 2 mol adduct, hydroquinone-ethylene oxide 2 mol adduct, -ethylene oxide 2 mol adduct, 2,2 ′
-Dihydroxybiphenyl-ethylene oxide 2 mol adduct, 4,4'-hydroxybiphenyl-ethylene oxide 2 mol adduct, p-hydroxyphenylethyl alcohol-ethylene oxide 2 mol adduct and the like. From the viewpoint of the phosphorus content in the compound, the formula weight of R1 is preferably small, and bisphenol A, bisphenol F, bisphenol S, hydroquinone, 2,2′-
Dihydroxybiphenyl and 4,4′-dihydroxybiphenyl are preferred.

In the chemical formula (1), at least one of X1 to X4 is a residue of a (substituted) styrenated phenol having a structure represented by the chemical formula (2), and other X1 to X4.
4 is the above chemical formula (3).

In the chemical formula (2), R2 is an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom, which may be the same or different. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group. Examples of the alkyl group substituted with a halogen atom include a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1,1, -dichloroethyl group, a 1,2-dichloroethyl group, and a 1,1,1-trichloroethyl group. Group, 2-chloropropyl group and the like. From the viewpoint of the phosphorus content of the compound, R2 is preferably a group having a small formula weight, and is preferably a hydrogen atom, a methyl group, an ethyl group or a chlorine atom.

In the chemical formula (2), the value of m is a number from 0 to 2. From the viewpoint of the compatibility of the compound with the resin, m
Is larger, and from the viewpoint of the phosphorus content of the compound, m is preferably smaller. In consideration of compatibility and phosphorus content, the value of m is preferably from 0 to 1.

R3 in the chemical formula (3) is an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom, which may be the same or different. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group. Examples of the alkyl group substituted with a halogen atom include a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1,1, -dichloroethyl group, a 1,2-dichloroethyl group, and a 1,1,1-trichloroethyl group. Group and a 2-chloropropyl group. R3 is preferably a group having a small formula weight from the viewpoint of the phosphorus content of the compound, and is preferably a hydrogen atom, a methyl group, an ethyl group, or a chlorine atom.

Specific examples of the phosphoric acid ester compound (A) of the present invention include chemical formulas (5), (6), (7),
The following compounds represented by (8) may be mentioned.

[0021]

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In the chemical formula (5), R4 and R5 are, for example, a hydrogen atom, a methyl group, an ethyl group, a chlorine atom and a chloromethyl group.

[0023]

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In the chemical formula (6), R7 and R8 are, for example, a hydrogen atom, a methyl group, an ethyl group, a chlorine atom and a chloromethyl group.

[0025]

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In the chemical formula (7), R9 is, for example, a hydrogen atom, a methyl group, an ethyl group, a chlorine atom or a chloromethyl group.

[0027]

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In the chemical formula (8), R10 and R11 are, for example, a hydrogen atom, a methyl group, an ethyl group, a chlorine atom and a chloromethyl group.

The phosphoric acid ester compound (A) of the present invention is
For example, it can be manufactured by the following two manufacturing methods.

The first manufacturing method will be described. A divalent diol containing an aromatic ring in the main chain [hereinafter referred to as a raw material (A)] is reacted with phosphorus oxyhalide to form an intermediate (a)
Get. At this time, the molar ratio of the raw material (a) to phosphorus oxyhalide is 1: 2 to 1:10, preferably 1: 2.
1: 4. At the time of the reaction, the raw material (A) and phosphorus oxyhalide may be mixed in advance, or one of them may be dropped into the other and reacted. Reaction temperature is 0 ° C
To 180 ° C, preferably 20 ° C to 160 ° C. The reaction time is 1 to 20 hours, usually 3 to 12 hours. As the raw material (A), specifically, bisphenol A, hydroquinone, 2,2′-dihydroxybiphenyl, 4,4′-hydroxybiphenyl, p-hydroxyphenylethyl alcohol; bisphenol A-ethylene oxide 2 mol adduct, hydroquinone -Ethylene oxide 2 mol adduct, 2,2'-dihydroxybiphenyl-ethylene oxide 2 mol adduct, 4,4'-
Examples include hydroxybiphenyl-ethylene oxide 2 mol adduct, p-hydroxyphenylethyl alcohol-ethylene oxide 2 mol adduct, and the like. Preferred are bisphenol A, hydroquinone, 2,2'-dihydroxybiphenyl and 4,4'-dihydroxybiphenyl. Examples of phosphorus oxyhalides include phosphorus oxychloride and phosphorus oxybromide. In the reaction, a known catalyst such as iron chloride, aluminum chloride or magnesium chloride may be used if necessary.

The intermediate (a) may be used as it is in the next reaction, but it is preferable to remove the unreacted phosphorus oxyhalide. Unreacted phosphorus oxyhalide can be easily removed by ordinary vacuum distillation.

Intermediate (a) and a (substituted) styrenated phenol represented by formula (9) wherein m is a number from 0 to 2, R2 is the same group as R2 in formula (2); A raw material (a)] and a phenol represented by the chemical formula (10) wherein R3 is the same group as R3 in the chemical formula (3);
After this, the raw material (c) is used] to obtain the phosphoric acid ester compound (A) of the present invention. The raw material (a) may be a single compound or a mixture of 2 to 4 types. The raw material (c) may be a single compound or a mixture of 2 to 3 types. The phosphate ester compound (A) to be produced
It is necessary to select according to the structure of

[0033]

[Chemical 12]

[0034]

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The raw material (a) can be obtained by reacting phenol with styrenes (styrene, substituted styrene, etc.). Here, styrenes are represented by the following chemical formula (1)
It has the structure shown in 1).

[0036]

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R2 in the chemical formula (11) is the chemical formula (2)
The same group as R2 in the above, an alkyl group having 1 to 6 carbon atoms,
They may be the same or different in either an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group. Examples of the alkyl group substituted with a halogen atom include a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1,1, -dichloroethyl group, a 1,2-dichloroethyl group, and a 1,1,1-trichloroethyl group. Group and a 2-chloropropyl group.
R2 is preferably a group having a small formula weight from the viewpoint of the phosphorus content of the compound, and is preferably a hydrogen atom, a methyl group, an ethyl group, or a chlorine atom. As the substituted styrene, styrene,
Examples include 3-methylstyrene, 3-chlorostyrene, 4-methylstyrene, 4-chlorostyrene, 3-ethylstyrene, and the like.

The molar ratio when the phenol and styrene are reacted is 1: 1 to 1: (1 + m) (m is 0 to
It is a number of 2 and is selected according to the structure of the phosphate compound to be produced). When the phenol and the styrenes are reacted, the phenol and the styrenes may be mixed in advance, or one of them may be dropped into the other and reacted. The reaction temperature is usually 80 to 140 ° C., preferably 80 ° C.
To 120 ° C., the reaction time is 2 to 10 hours, usually 2 to
6 hours. A catalyst may be added to promote the reaction during the reaction. As the catalyst, a protic acid such as methanesulfonic acid and a Lewis acid such as aluminum chloride can be used. The amount of the catalyst used is usually 0.1 to 5.0 mol% based on phenol.

The raw material (C) is a compound represented by the formula (10), and R3 in the chemical formula (10) is the same as R3 in the chemical formula (3).
It represents the same group as 3, and may be the same or different from any of an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom and a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group. Examples of the alkyl group substituted with a halogen atom include a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1,1, -dichloroethyl group, a 1,2-dichloroethyl group, and a 1,1,1-trichloroethyl group. Group and a 2-chloropropyl group. R3
Is preferably a group having a small formula weight from the viewpoint of the phosphorus content of the compound, and is preferably a hydrogen atom, a methyl group, an ethyl group, or a chlorine atom. Raw materials (c) include phenol and 4-
Chlorophenol, 4-methylphenol (p-cresol), 4-ethylphenol and the like can be mentioned.

When the intermediate (a) is reacted with the raw material (a) and the raw material (c), the molar ratio of the intermediate (a) and the [total amount of the raw material (a) + the raw material (c)] Is 1: 4 to 1:20. The molar ratio between the raw material (a) and the raw material (c) must be selected according to the structure of the phosphate ester to be produced.
Raw material (a): raw material (c) (molar ratio) is 4: 0, 3:
1, 2: 2, 1: 3. At the time of the reaction, the intermediate (a), the raw material (a) and the raw material (c) may be mixed in advance, or the intermediate (a) may be added dropwise to the raw material (a) and the raw material (c). Alternatively, the raw material (a) and the raw material (c) may be dropped and reacted on the intermediate (a). The reaction temperature is 0 ° C to 180 ° C, preferably 20 ° C to 160 ° C.
° C. The reaction time is 1 hour to 20 hours, usually 3 hours to 12 hours. In the reaction, a known catalyst such as iron chloride, aluminum chloride or magnesium chloride may be used if necessary.

Since the unreacted raw material reduces the flame retardancy of the obtained phosphoric acid ester compound, it is better to use it after purification. Purification can be performed by a usual organic synthesis technique. For example, there is the following method. The first purification method is to remove unreacted raw material (a) and raw material (c) by ordinary vacuum distillation. The temperature of vacuum distillation is 100
C. to 250.degree. C., and the degree of pressure reduction is 2 mmHg to 400 mmHg.

The second purification method is ordinary water washing or alkaline water washing. After sufficiently mixing the obtained phosphoric acid ester compound and alkaline water or water, the mixture is allowed to stand and separate to obtain a phosphoric acid ester compound from the organic layer. To promote liquid separation,
An organic solvent such as chloroform may be added. The organic layer is dried by an ordinary method, and when an organic solvent such as chloroform is added, it is removed by ordinary vacuum distillation to obtain a purified phosphate compound.

Next, a second manufacturing method will be described. The above-mentioned intermediate (a) is obtained in the same manner as in the first production method. Intermediate (a) is reacted with phenol and the raw material (C) to obtain intermediate (b). The raw material (c) is the same compound as the raw material (c) in the first production method.
A mixture of three types may be used and can be freely selected depending on the structure of the phosphate ester to be produced.

When reacting the intermediate (a) with phenol and the raw material (c), the molar ratio of the intermediate (a) and [total amount of phenol + raw material (c)] is 1: 4 to 1: 20. The molar ratio between phenol and the raw material (c) must be selected according to the structure of the phosphate ester to be produced. Usually, the phenol: raw material (c) (molar ratio) is 4: 0.
3: 1.2: 2.1: 3. During the reaction, the intermediate (a) may be mixed with the phenol and the raw material (c) in advance. Alternatively, the intermediate (a) may be added dropwise to the phenol and the raw material (c), and the phenol and the raw material (c) may be added. (C) may be added dropwise to the intermediate (a) for reaction. The reaction temperature is 0 ° C to 180 ° C, preferably 20 ° C to 160 ° C.
° C. The reaction time is 1 hour to 20 hours, usually 3 hours to 12 hours. In the reaction, a known catalyst such as iron chloride, aluminum chloride or magnesium chloride may be used if necessary.

The obtained intermediate (b) may be used as it is in the next reaction, but it is preferable to remove unreacted phenol and the raw material (c). Unreacted phenol and raw material (c) can be easily removed by ordinary vacuum distillation.

The phosphate compound (A) of the present invention can be obtained by reacting the obtained intermediate (b) with styrenes. The styrenes used are the first
Is the same compound as the styrenes in the production method, and may be one kind or a plurality of kinds, and is selected from the structure of the phosphate (A) to be produced. As styrenes, styrene, 3-methylstyrene, 3-chlorostyrene, 4-
Methyl styrene, 3-chloro styrene, 3-ethyl styrene, etc. are mentioned.

The molar ratio when the intermediate (b) is reacted with styrenes is 1: 1 to 1: (4 + 4 m) (m
Is a number from 0 to 2 and is selected according to the structure of the phosphate compound to be produced). When the intermediate (b) and the styrenes are reacted, the intermediate (b) and the styrenes may be mixed in advance, or either one may be dropped into either one to be reacted. The reaction temperature is usually 80 to 140.
℃, preferably 80 ℃ ~ 120 ℃, the reaction time is 2
It is 10 hours, usually 2 to 6 hours. A catalyst may be added to promote the reaction during the reaction. As a catalyst,
Protonic acids such as methanesulfonic acid and Lewis acids such as aluminum chloride can be used. The amount of catalyst used is
Usually, it is 0.1 to 5.0 mol% with respect to the intermediate (b).

Since the unreacted raw material reduces the flame retardancy of the obtained phosphoric acid ester compound, it is better to use it after purification, and it can be purified in the same manner as in the first production method.

As a second aspect of the present invention, the obtained phosphate ester compound (A) is used as an essential component, and a flame retardant (B)
Can be obtained. As a synthetic resin, an effect is recognized when used for a general synthetic resin, but a remarkable effect is recognized for a synthetic resin containing an aromatic ring, such as a polystyrene resin, an ABS resin, a polycarbonate resin, and a polyphenylene ether resin. Can be The same effect is obtained for these blend resins.

As the third aspect of the present invention, the flame retardancy-imparting agent (B)
And a flame-retardant resin composition (C) comprising one or more resins selected from the group consisting of polystyrene resin, ABS resin, polycarbonate resin and polyphenylene ether resin
Get. Polystyrene resin, ABS resin, polycarbonate resin, polyphenylene ether resin and the like can be used by blending them in an appropriate ratio depending on the physical properties of the intended resin, which will be referred to as resin (I). The blending ratio of the resin (I) and the flame retardant imparting agent (B) is not particularly limited as long as the effects of the invention can be sufficiently exhibited, but the blending ratio of the flame retardant imparting agent (B) is low. If it is too large, the flame retardance is insufficient, and if it is too large, the tensile strength and heat resistance of the resin are impaired. The blending ratio is such that the flame retardant (B) is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the resin (I).

Other additives to the resin composition of the present invention, such as plasticizers, other flame retardants, antioxidants and ultraviolet absorbers, stabilizers, mold release agents, etc., within the range of not impairing the effects of the present invention. Agents, pigments, fibrous reinforcing materials such as glass fiber and carbon fiber,
Fillers such as glass beads, calcium carbonate, and talc can be added. The method for producing the resin composition of the present invention is not particularly limited, an extruder, a heating roll,
It can be kneaded and manufactured using a kneader such as a kneader.

[0052]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

[0053]

【Example】

Example 1 In a reaction container capable of heating and stirring, 188 g of phenol,
3.76 g of methanesulfonic acid was charged as a catalyst and heated to 100 ° C. with stirring. When the temperature reached 100 ° C., 208.3 g of styrene was added dropwise over 2 hours for reaction. Then, it was aged for 1 hour and cooled to room temperature to obtain 396.3 g of styrenated phenol. In a reaction vessel capable of heating and stirring, 291.7 g of phosphorus oxychloride and 144.4 g of bisphenol A were charged and stirred.
Heated to 0 ° C. Thereafter, it was aged for 7 hours. Then 140
The temperature inside the reaction vessel was gradually reduced while maintaining the temperature at 0 ° C., and finally the pressure was set to 20 mmHg, and unreacted phosphorus oxychloride was removed over 4 hours. Subsequently, with stirring, 126.5 g of phenol and 266.5 g of the styrenated phenol obtained above were added dropwise over 4 hours. Subsequently, it was gradually heated to 140 ° C. and aged at that temperature for 4 hours. Subsequently, while maintaining the temperature at 140 ° C., the pressure in the reaction vessel was gradually reduced to a pressure of 5 mmHg, and unreacted phenol and styrenated phenol were removed over 8 hours. Then, it cooled to room temperature. The obtained product was washed and separated four times with 400 g of pure water, the organic layer was dehydrated using a rotary evaporator, and the phosphate compound (2,2-bis (4- (phenoxy-4- (α) -Phenyl-ethyl) phenoxy-phosphinyloxy) phenyl) propane) 496.0 g
Was obtained (yield 87%; converted to bisphenol A). Table 1 shows the ¹ H-NMR chemical shift δ value (solvent: CDCl ₃ ) measurement results and the elemental analysis measurement results of the obtained phosphate compound. ¹ H-NMR: δ 1.60 (s, 6H), 1.66 (m, 6H), 4.11 (q, 1H),
4.42 (q, 1H), 6.69〜7.37 (m, 36)

[0054]

[Table 1]

Example 2 The same procedure as in Example 1 was repeated except that 69.7 g of hydroquinone was used instead of 144.4 g of bisphenol A, and the phosphoric ester compound (1,4-bis (4- ( Phenoxy-4- (2-phenyl-ethyl) phenoxy-phosphinyloxy) benzene) 421.0
g was obtained (yield: 85%; calculated as hydroquinone). Table 2 shows the measurement results of the ¹ H-NMR chemical shift δ value (solvent: CDCl ₃ ) of the obtained phosphate ester compound and the measurement results of the elemental analysis. ¹ H-NMR: δ 1.66 (m, 6H), 4.11 (q, 1H), 4.42 (q, 1H),
6.69 to 7.37 (m, 32)

[0056]

[Table 2]

Example 3 In Example 1, 3 instead of 208.3 g of styrene was used.
Example 1 with the exception of using 236.3 g of methylstyrene.
Similarly to, 3-methylstyrenated phenol 39
8.8 g are obtained. In Example 1, except that instead of 266.5 g of styrenated phenol, 285.3 g of 3-methylstyrenated phenol obtained above was used,
Phosphate ester compound (2,2-bis (4- (phenoxy-4- (α- (3-methylphenyl) -ethyl) phenoxy-phosphinyloxy) phenyl) propane) 4
93.7 g was obtained (yield: 84%; in terms of bisphenol A). Table 3 shows the measurement results of the ¹ H-NMR chemical shift δ value (solvent: CDCl ₃ ) of the obtained phosphoric acid ester compound and the measurement results of the elemental analysis. ¹ H-NMR: δ 1.60 (s, 6H), 1.66 (m, 6H), 2.22 (s, 6H),
4.11 (q, 1H), 4.42 (q, 1H), 6.69 ~ 7.37 (m, 34)

[0058]

[Table 3]

Example 4 In a reaction container capable of heating and stirring, 188 g of phenol,
3.76 g of methanesulfonic acid was charged as a catalyst and heated to 100 ° C. with stirring. When the temperature reached 100 ° C., 416.6 g of styrene was added dropwise over 2 hours for reaction. Thereafter, the mixture was aged for 1 hour and cooled to room temperature. The reaction product was filtered with a pressure filter to remove the activated clay of the catalyst to obtain 604.6 g of distyrenated phenol. Phosphorus oxychloride 291.7 in a reaction vessel capable of heating and stirring.
g and bisphenol A (144.4 g) were charged and heated to 140 ° C. with stirring. Thereafter, it was aged for 7 hours. Subsequently, the pressure in the reaction vessel was gradually reduced while maintaining the temperature at 140 ° C., so that the pressure finally reached 20 mmHg, and unreacted phosphorus oxychloride was removed over 4 hours. Subsequently, with stirring, 126.5 g of phenol and 406.6 g of the distyrenated phenol obtained above were added dropwise over 4 hours. Then, it aged at 140 degreeC for 4 hours. Subsequently, the pressure inside the reaction vessel was gradually reduced while maintaining the temperature at 140 ° C., so that the pressure finally reached 5 mmHg, and unreacted phenol and dithylene phenol were removed over 8 hours. Then, it cooled to room temperature. The obtained product was washed and separated four times with 400 g of pure water, and the organic layer was dehydrated using a rotary evaporator to obtain a phosphate compound (2,2-bis (4- (phenoxy-4).
-(Α- (4- (α-phenylethyl) -phenyl)-
Ethyl) phenoxy-phosphinyloxy) phenyl)
582.4 g of propane) was obtained (83% yield; bisphenol A conversion). ¹ H of the obtained phosphoric acid ester compound
Table 4 shows the measurement results of the NMR chemical shift δ value (solvent: CDCl ₃ ) and the measurement results of the elemental analysis. ¹ H-NMR: δ 1.60 (s, 6H), 1.66 (m, 12H), 4.11 (q, 2
H), 4.42 (q, 2H), 6.69 ~ 7.37 (m, 44)

[0060]

[Table 4]

Example 5 The intrinsic viscosity [η] measured at 30 ° C. in chloroform was 0.
52 parts of poly 2,6-dimethyl-1,4-phenylene ether (hereinafter abbreviated as PPE) 65 parts and polystyrene resin [Asahi Kasei Kogyo KK: Asahi Kasei polystyrene 68]
5] (hereinafter abbreviated as PS) To 100 parts by weight of a total of 35 parts of the resin composition, 20 parts by weight of the phosphoric acid ester compound obtained in Example 1 was mixed, and a cylinder temperature of 300
Pellets were obtained by melt-kneading with a twin-screw extruder set to ° C. Injection molding was performed using this pellet to obtain a test piece. This test piece was used for evaluation. The results are shown in Table 5.

Example 6 Evaluations were made in the same manner except that the phosphoric acid ester in Example 5 was replaced with the phosphoric acid ester compound obtained in Example 2. The results are shown in Table 5.

Example 7 Evaluations were made in the same manner except that the phosphate ester compound obtained in Example 5 was replaced with the phosphate ester compound obtained in Example 3. The results are shown in Table 5.

Example 8 Evaluations were made in the same manner except that the phosphate ester compound obtained in Example 5 was replaced with the phosphate ester compound obtained in Example 4. The results are shown in Table 5.

Comparative Example 1

The evaluation was performed in the same manner as in Example 5 except that the phosphoric ester was changed to triphenyl phosphate. The results are shown in Table 5.

Comparative Example 2 The phosphoric acid ester in Example 5 was replaced by the following chemical formula (1)
Evaluation was carried out in the same manner except that the compound 2) [produced by the method described in JP-A-6-228426] was used. The results are shown in Table 5.

[0068]

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[0069]

[Table 5] A rating of V-0 in the flame retardancy test (UL94 assessment) indicates that the flame retardancy of a typical synthetic resin is acceptable.

Example 9 Polycarbonate resin [manufactured by Sumitomo Nogadak Co., Ltd .: C
22 parts by weight of the phosphoric acid ester compound obtained in Example 1 with respect to a total of 100 parts by weight of a resin composition of 50 parts of ALIBRE300-6 and 50 parts of ABS resin [Clarastic MTA manufactured by Sumitomo Nogaduck Co., Ltd.]. Were mixed and melt-kneaded with a twin-screw extruder having a cylinder temperature of 240 ° C. to obtain pellets. Injection molding was performed using this pellet to obtain a test piece. Evaluation was performed using this test piece.
Table 6 shows the results.

Example 10 Evaluation was carried out in the same manner as in Example 9 except that the phosphate ester compound obtained in Example 2 was used instead of the phosphate ester compound. Table 6 shows the results.

Example 11 Evaluation was performed in the same manner as in Example 9 except that the phosphate ester compound obtained in Example 3 was used instead of the phosphate ester compound. Table 6 shows the results.

Example 12 Evaluation was performed in the same manner as in Example 9 except that the phosphate ester compound obtained in Example 4 was used instead of the phosphate ester compound. Table 6 shows the results.

Comparative Example 3 Evaluation was carried out in the same manner as in Example 9 except that the phosphoric ester was changed to triphenyl phosphate. Table 6 shows the results.

Comparative Example 4 The phosphoric ester of Example 5 was replaced with the above-mentioned chemical formula (1)
Evaluation was carried out in the same manner except that the compound 2) [produced by the method described in JP-A-6-228426] was used. Table 6 shows the results.

[0076]

[Table 6] In the evaluation of the flame retardancy test (UL94 judgment), V-0 grade indicates that the flame retardancy of a general synthetic resin is acceptable.

[0077]

Industrial Applicability The novel phosphoric acid ester compound of the present invention is very useful as a flame retardant imparting agent for polystyrene resin, ABS resin, polycarbonate resin, polyphenylene ether resin and blended resins thereof. When blended with a resin as a flame retardant, the compound of the present invention has good compatibility with the resin and can impart flame retardancy to the resin without deteriorating the transparency and the physical properties of the resin.

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Claims (8)

[Claims] 1. A compound represented by the general formula (1): [Wherein R 1 is a residue of a diol containing an aromatic ring in the main chain; at least one of X 1 to X 4 is represented by the following chemical formula (2): A residue of a (substituted) styrenated phenol having a structure represented by the formula (wherein R2 is an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom). , M may be the same or different; m is a number from 0 to 2), and other X1 to X4 are represented by the following chemical formula (3): A (substituted) phenyl group having a structure represented by the formula (in the formula, R3 is an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, a halogen atom or a hydrogen atom, which may be the same or different. The phosphoric ester compound (A). 2. The phosphorus according to claim 1, wherein R1 is a residue of one or more diols selected from the group consisting of bisphenols, hydroquinones, biphenols, hydroxyphenylalkyl alcohols and alkylene oxide adducts thereof. Acid ester compounds. 3. The phosphate compound according to claim 1, wherein R1 is a residue of 2,2-bis (4-hydroxyphenyl) propane. 4. The compound according to claim 1, wherein R2 is a hydrogen atom. 5. The method according to claim 1, wherein m in formula (2) is 0.
4. The phosphoric acid ester compound according to any one of to 4. 6. The method according to claim 1, wherein X1 and X3 are phenyl groups.
6. The phosphate compound according to any one of items 1 to 5. 7. A flame retardant for synthetic resin (B), comprising the phosphoric ester compound (A) according to claim 1 as an essential component. 8. The flame retardant imparting agent (B) according to claim 7,
A flame-retardant resin composition (C) comprising one or more resins selected from the group consisting of polystyrene resin, ABS resin, polycarbonate resin and polyphenylene ether resin.