JPH11240849A - Bromine compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a highly pure bromine compound excellent in heat stability by reacting a solution obtained by dissolving a compound having an aliphatic unsaturated bond in a halogenated aliphatic hydrocarbon solution with a bromine-mixed solution in the presence of a specific compound having hydroxy group. SOLUTION: This method for producing a bromine compound by mixing and reacting a solution of (A) a compound of the formula R<1> -O-Ar<1> -Y-Ar<2> -O-R<2> (Ar<1> and Ar<2> are each a 5-16C aromatic hydrocarbon or the like; Y is sulfone or the like; R<1> and R<2> are each a 2-11C hydrocarbon having an aliphatic unsaturated group), e.g. 2,2-bis[(3,5-dibromo-4-allyloxy)phenyl]propane} dissolved in (B) a halogenated aliphatic hydrocarbon solvent with bromine or a solution of the bromine comprises using (C) a compound of the formula R<5> -(OH)u [R<5> is a (u)-valent 1-6C aliphatic group; (u) is 1-4] in an amount corresponding to 0.5-20 hydroxy groups based on 100 unsaturated groups of the component A in the bromine-mixed solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bromine compound obtained by brominating a compound containing an aliphatic unsaturated bond and a method for producing the same.

[0002]

2. Description of the Related Art Generally, in the field of organic chemistry, a bromination reaction to an aliphatic unsaturated group is a reaction that is frequently employed when synthesizing a brominated derivative. Due to the intensity of the reaction, it is essential to remove the reaction heat from within the reaction system.For this reason, the operation of cooling the reaction system and adding bromine over time in a mild state is generally adopted. ing.

[0003] For example, JP-A-50-30853,
JP-A-55-111429, JP-A-7-1730
No. 92, 2,2-bis {(3,5-dibromo-
The reaction of 4-allyloxy) phenyl} propane with bromine describes a method in which bromine is added dropwise at a temperature of about 20 ° C.

In Japanese Patent Application Laid-Open No. 7-316087, as a specific example, a reaction with a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is performed by using a cooling tube. 24 to 27 ° C
And a method of dropping bromine over 1 hour while controlling the temperature.

On the other hand, for example, Japanese Patent Publication No. 50-23693 discloses, as a specific example, bis {(3,5-dibromo-
In bromination of 4-allyloxy) phenyl disulfone, a method is disclosed in which such a compound is dissolved in methylene chloride and bromine is reacted with the compound at the boiling point of methylene chloride.

The bromination of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone is described in JP-A-3-271267 and JP-A-4-234.
As disclosed in JP-A-354-354, specifically, the former is a method in which bromine is dropped at 39 ° C. or 40 ° C. over 1 hour to a methylene chloride solution of the compound, and the latter is bromine at 35 to 39 ° C. For 1.5 hours.

However, in these methods,
At the time of such bromination reaction, along with the generation of the desired bromine compound, the generation of a by-product also occurs. When used as a flame retardant, there are problems such as a decrease in the thermal stability of such a resin.

[0008]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a bromine compound having a high purity and excellent heat stability by reacting a compound having an aliphatic unsaturated bond with bromine and a method for producing the same. As a result of diligent studies, during the bromination reaction, the water contained in a solution of a compound having an aliphatic unsaturated bond dissolved in a halogenated aliphatic hydrocarbon solvent and bromine or a mixed solution of a bromine solution, It has been found that a reaction takes place and that such by-products derived from water reduce the thermal stability of the bromine compound.

However, although the amount of water in the mixed solution can be reduced to some extent, the thermal stability of the obtained bromine compound is still insufficient, and in order to reduce the amount of water, there are restrictions on equipment and operation. Many were inconvenient. Therefore, as a result of further research, a solution in which a compound having an aliphatic unsaturated bond is dissolved in a halogenated aliphatic hydrocarbon solvent is mixed with bromine or a bromine solution, and when the bromination is caused by the reaction, the compound has a hydroxyl group. The inventors have found that the above objects can be achieved by using specific compounds, and have reached the present invention.

[0010]

According to the present invention, there is provided, according to the present invention, a solution of a compound having an aliphatic unsaturated bond represented by the following formula (1) in a halogenated aliphatic hydrocarbon solvent: bromine or bromine; A method for producing a bromine compound represented by the following formula (2) by mixing and reacting with a solution:
For the compound having an aliphatic unsaturated bond, a compound having a hydroxyl group represented by the following formula (3) per 100 unsaturated groups corresponds to a compound having a hydroxyl group number of 0.5 to 20. The present invention provides a method for producing a bromine compound, which comprises reacting the bromine compound in an amount.

[0011]

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(In the formula, Ar ¹ and Ar ² may be the same or different and represent an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms. The hydrogen group may be substituted by at least one halogen atom, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single atom. Represents a bond, R
¹ and R ² may be the same or different and represent a C ^{2 to} C 11 hydrocarbon group having at least one aliphatic unsaturated group, and one of R ¹ and R ² is an unsaturated group May be added by a halogen atom. )

[0013]

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(Wherein Ar ¹ , Ar ² and Y have the same meanings as defined in the above formula (1). R ³ and R ⁴ each represent an unsaturated group in R ¹ and R ² in the above formula (1) Means a group wherein the group is saturated by a bromine atom.)

[0015]

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(Wherein, R ⁵ represents a u-valent aliphatic group having 1 to 6 carbon atoms, and u represents an integer of 1 to 4).

The compound having an aliphatic unsaturated bond used in the method of the present invention is represented by the above formula (1). In the above formula (1), Ar ¹ and Ar ² may be the same or different and each have an aromatic hydrocarbon group having 5 to 16 carbon atoms, preferably 6 to 12 carbon atoms, or 5 to 12 carbon atoms, preferably 5 to 12 carbon atoms. It is a saturated alicyclic hydrocarbon group having 6 to 10 carbon atoms. It is industrially advantageous that Ar ¹ and Ar ² are the same and are aromatic hydrocarbon groups. Specific examples of Ar ¹ and Ar ² include 1,4-phenylene group, 1,4-methylphenylene group, 1,4-dimethylphenylene group, 2,6-
A naphthylene group and a 2,7-naphthylene group;
A 4-phenylene group is preferred.

In these Ar ¹ and Ar ² , the carbon atom forming the hydrocarbon may be substituted with a halogen atom. Particularly, for the purpose of producing a flame retardant, a halogen atom, especially a bromine atom Is preferably substituted.
The number of halogen atoms substituted for each of Ar ¹ and Ar ² is preferably 1 to 6, preferably 2 to 4, with respect to Ar ¹ (or Ar ² ).

In the above formula (1), Y is a group or a bond connecting Ar ¹ and Ar ² and has 1 to 6 carbon atoms;
Preferably a saturated hydrocarbon group having 1 to 3 carbon atoms; sulfone group (-SO ₂ -); sulfide groups (-S-); ketone group (-CO-); 2 to 6 carbon atoms, preferably 2 to carbon atoms 4
Or an alkylene oxide group of the formula: or a single bond.
Desirable Y is a methylene group, an isopropylidene group, a cyclohexylidene group, a sulfone group, a sulfide group, a ketone group or a single bond.

In the above formula (1), R ¹ and R ² may be the same or different and have 2 to 11 carbon atoms having at least one aliphatic unsaturated group, preferably 2 to 2 carbon atoms.
5 represents a hydrocarbon group, and any one of R ¹ and R ² may have a part of the unsaturated group added by a halogen atom, preferably a bromine atom. Specific examples of R ¹ and R ² are preferably a vinyl group, an allyl group and an isobutenyl group.

As the compound having an aliphatic unsaturated bond represented by the above formula (1) of the present invention, specifically, 2,2-
Bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2,2-bis} (3,5-dibromo-4
-Isobutenyloxy) phenyl {propane, bis {(3,5-dibromo-4-allyloxy) phenyl}
Methane, bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane, (3,3 ', 5,5'-tetrabromo-4,4'-diallyloxy) biphenyl,
(3,3 ', 5,5'-Tetrabromo-4,4'-divinyloxy) biphenyl, bis {(3,5-dibromo-
4-allyloxy) phenyl} sulfone and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone, among which 2,2-bis} (3,5-dibromo-4- Allyloxy) phenyl {propane, 2,2-bis} (3,5-dibromo-4)
-Isobutenyloxy) phenyl {propane, bis {(3,5-dibromo-4-allyloxy) phenyl}
Methane, bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane, (3,3 ', 5,5'-tetrabromo-4,4'-diallyloxy) biphenyl and (3,3' , 5,5'-Tetrabromo-4,4'-
Divinyloxy) biphenyl is preferred,
2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3,5- Dibromo-4-allyloxy) phenyl
Methane and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane are more preferred, and 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is particularly preferred. You.

The solvent used for dissolving the compound having an aliphatic unsaturated bond in the method of the present invention is a halogenated aliphatic hydrocarbon. Such a solvent is preferably as high as possible in solubility for a compound having an aliphatic unsaturated bond, but may be partially soluble. Further, it is preferable that the bromine compound produced by the bromination reaction of the compound having an aliphatic unsaturated bond substantially dissolves in the solvent.

The solvent in the method of the present invention is not only used as a mere solvent for performing the reaction uniformly, but also preferably functions as a solvent for effectively removing the heat of reaction out of the reaction system. have. So the solvent is
Those having a normal pressure boiling point of 0 to 100 ° C, preferably 20 to 90 ° C, are advantageous. Especially 2
Those having a range of 0 to 60 ° C are desirable.

Examples of the halogenated aliphatic hydrocarbon solvent include methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, and acetone chloride. And chloroform are preferred, and methylene chloride is particularly preferred. These solvents are used alone or in combination of two or more. These halogenated hydrocarbons can also be used as a mixed solvent with dioxane.

In the method of the present invention, bromine or a bromine solution is used. As the solvent used in the bromine solution, the same solvent as described above is used, and in this case, the concentration of bromine is preferably in the range of 10 to 90% by weight.

These solvents correspond to 2 to 1000 solvent molecules per unsaturated group in the compound having an aliphatic unsaturated bond represented by the above formula (1). It is used in an amount, preferably in an amount corresponding to 2.5 to 800 solvent molecules. In the bromination reaction of the present invention, since it is a preferred embodiment that a substantial amount of the reaction heat is removed to the outside of the reaction system by the heat of vaporization of the solvent, the solvent more preferably corresponds to the number of 3 to 700 solvent molecules. It is advantageous to use an amount which corresponds to the number of solvent molecules, particularly preferably from 4 to 600 solvent molecules.

In the method of the present invention, a solution in which a compound having an aliphatic unsaturated bond is dissolved in a halogenated aliphatic hydrocarbon and bromine or a bromine solution are mixed, and the compound having an aliphatic unsaturated bond is mixed with bromine. And react. In this bromination reaction, it is necessary to use a compound having a hydroxyl group represented by the above formula (3). The compound having a specific hydroxyl group is present in a solution obtained by mixing a solution of a compound having an aliphatic unsaturated bond with bromine or a bromine solution, whereby an active intermediate and a fat formed by a reaction between water and bromine are produced. The reaction of the compound having an aliphatic unsaturated bond with an aliphatic unsaturated group is suppressed, and the active intermediate formed by the reaction of the compound having a hydroxyl group with bromine is used as the fatty acid of the compound having an aliphatic unsaturated bond. By-products formed by reacting with the group-unsaturated group do not adversely affect the thermal stability of the bromine compound, so that the resulting bromine compound has good thermal stability.

The compound having a hydroxyl group used in the method of the present invention is a compound represented by the above formula (3), wherein R ⁵ is a u-valent aliphatic group having 1 to 6 carbon atoms, preferably a u-valent. C1-C6 aliphatic hydrocarbon group, C1-C4
Is an oxygen-containing saturated hydrocarbon group or a sulfur-containing saturated hydrocarbon group, and u is an integer of 1 to 4, preferably 1 or 2. Specifically, methanol, ethanol, n-
Propanol, i-propanol, n-butanol, i
-Butanol, sec-butanol, tert-butanol, allyl alcohol, ethylene glycol and diethylene glycol, among which methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol and tert -Butanol is preferred, especially methanol, ethanol and i-propanol.

The compound having a hydroxyl group is different from the compound having an aliphatic unsaturated bond in that the unsaturated group 10
An amount corresponding to 0.5 to 20, preferably 0.8 to 18, more preferably 1 to 15, particularly preferably 1 to 10, hydroxyl groups per 0 is used. When the amount of the compound having a hydroxyl group is less than the amount corresponding to 0.5 hydroxyl groups per 100 unsaturated groups of the compound having an aliphatic unsaturated bond, water and bromine When the reaction between the active intermediate produced by the reaction and the compound having an aliphatic unsaturated bond proceeds easily, the thermal stability of the resulting bromine compound decreases, which is not preferable. An active intermediate produced by the reaction of a compound having a hydroxyl group with bromine has an increased amount of by-products produced by reacting with a compound having an aliphatic unsaturated bond, and the purity of the obtained bromine compound is insufficient. Further, such a bromine compound is not preferable because it has a bad influence on the flame retardancy of the resin composition in which the resin composition is blended with the resin as a flame retardant.

In the method of the present invention, the method of mixing a solution of a compound having an aliphatic unsaturated bond in a halogenated aliphatic hydrocarbon solvent with bromine or a bromine solution is not particularly limited. A method of adding and mixing a bromine solution to a solution of a compound having an aliphatic unsaturated bond, a method of adding and mixing a solution of a compound having an aliphatic unsaturated bond to bromine or a bromine solution, or a method of adding bromine or a bromine solution and a fat A method of simultaneously adding a solution of a compound having a group unsaturated bond to a reactor and mixing the solutions can be adopted.

In a static mixer having 4 to 20 elements, the flow rate of a solution of a compound having an aliphatic unsaturated bond dissolved in a halogenated aliphatic hydrocarbon solvent and bromine or a mixed solution of bromine is 15 cm / A method in which the mixture is introduced so as to have a speed of at least 2 seconds and the residence time in the static mixer is set to 180 seconds or less, and then the mixture is charged into a reactor having a capacity 30 times or more the capacity of the static mixer. It can also be used. By using a static mixer as a mixer, mixing can be efficiently performed in a short time, and a high-purity bromine compound can be obtained with a high yield.

In the method of the present invention, it is preferable to employ a method in which a substantial amount of the heat of bromination is removed by a solvent or heat of vaporization of bromine during the bromination reaction. A method of cooling and liquefying by means of a condenser or the like provided at the top and returning it to the reaction system again, that is, a method of refluxing is preferred because of easy operation and easy operation. By employing such a method, the produced bromine compound becomes higher in purity and excellent in thermal stability. Simply reacting a compound having an aliphatic unsaturated bond with bromine at a high temperature easily generates by-products and lowers the purity as compared with the reaction at a low temperature, but in such a method, a high purity A bromine compound can be obtained. this is,
It is considered that the compound having an aliphatic unsaturated bond and bromine are uniformly dispersed in the system due to the stirring effect by the reflux, and the side reaction is less likely to occur. Here, the substantial amount of heat of reaction means at least 80%, preferably at least 85% of the theoretical calorific value generated by the desired bromination reaction.

The bromination reaction of the present invention is not limited to normal pressure, and can be carried out under pressure or under reduced pressure. The reaction temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher. Further, when the boiling point of the solvent used is lower than the boiling point of bromine, the reaction temperature can be increased by applying pressure, and when the boiling point of the solvent used is higher than the boiling point of bromine, the reaction is performed by reducing the pressure. The temperature can be lowered. Thus, the reaction temperature in the bromination reaction of the present invention is:
The type of solvent (boiling point) used and the amount of bromine can be controlled by operating pressure. Normal,
The reaction temperature is advantageously in the range from 0 to 60 ° C, preferably in the range from 5 to 55 ° C, particularly preferably in the range from 10 to 50 ° C.

The production method of the present invention is a so-called batch method, in which a certain amount is added to a reactor to terminate the bromination reaction,
It is also possible to carry out a post-treatment such as removal of residual excess bromine, which will be described later, in the same reactor.In addition, a reaction solution is appropriately drawn out from the reactor for performing the bromination reaction, and the post-treatment is performed in another container. It is also possible to do. Furthermore, the method of the present invention allows the bromination reaction to be performed continuously, and while continuously introducing the raw materials, providing a take-out port in a part of the reactor to draw out a part of the reaction solution. It can be continuously taken out to another container and post-processed. Further, a part of the derived reaction solution may be circulated.

The amount of bromine used in the method of the present invention may be a sufficient amount for the compound having an aliphatic unsaturated bond to obtain a desired bromine compound. An amount corresponding to the number of bromine molecules, preferably 1 to 5 per unsaturated group in the compound having
More preferably, bromine is used in an amount corresponding to the number of 1 to 3 bromine molecules.

In the bromination reaction of the present invention, as described above, the compound having a hydroxyl group represented by the above formula (3) is
By causing a solution of the compound having an aliphatic unsaturated bond and bromine or a bromine solution to be present in a mixed reaction solution, generation of by-products due to moisture is suppressed. However, if the amount of water present in the mixed reaction solution is too large, a large amount of the compound having the hydroxyl group is used in order to suppress a side reaction due to moisture. Therefore, as described above, the hydroxyl group is used. An active intermediate produced by the reaction of a compound having the formula (I) and bromine, by-products reacted with the compound having an aliphatic unsaturated bond will be produced in large amounts, the purity of the resulting bromine compound will be insufficient, The flame retardancy of a resin composition containing such a bromine compound as a flame retardant in a resin is adversely affected. Therefore, the concentration of water in the solution of the compound having an aliphatic unsaturated bond during the bromination reaction, the concentration of water in the reaction solution substantially consisting of bromine or a bromine solution and the compound having a hydroxyl group has an aliphatic unsaturated bond. It is preferable that the number of water molecules per 100 unsaturated groups of the compound is equivalent to 10 or less, and 0.05 to 1
The range of the amount corresponding to 0 is more preferable, and 0.05 to 5
The range of the amount corresponding to the number is more preferable. Such a water content is measured by the Karl Fischer method.

As a method for adjusting the amount of water to be removed, a method in which a solvent to be used is brought into contact with anhydrous calcium carbonate, anhydrous calcium chloride, anhydrous sodium sulfate, or the like. There are a method of contact mixing and a contact treatment with a water-absorbing desiccant such as phosphorus pentoxide, molecular sieve, and the like. It is also necessary to prevent steam from entering the reactor.

The desired bromine compound can be separated and recovered from the reaction mixture obtained by the above-mentioned bromination reaction by a method known per se. However, unreacted bromine remains in the reaction mixture. Therefore, the method of treating residual bromine with a reducing agent, converting bromine into hydrobromic acid once, and then adding an alkaline neutralizing agent is usually used. Has been adopted.

As the reducing agent used in such a treatment,
It is a reducing agent used in a normal reduction reaction, specifically, sodium bisulfite, sodium dithionite,
Sodium sulfite, oxalic acid, hydrogen sulfide, sodium nitrite, potassium nitrite, hydroxylamine sulfate, tin, stannous oxide, hydrazine, and the like; sodium bisulfite, sodium dithionite, sodium sulfite, oxalic acid, Sodium nitrate is preferably used. These reducing agents can also be used as an aqueous solution. These reducing agents are used alone or in combination of two or more.

Examples of the alkaline neutralizer include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates. ,Sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, calcium carbonate, and the like are preferable, and sodium hydroxide is particularly preferably used. These alkaline neutralizing agents are preferably used as an aqueous solution. These alkaline neutralizing agents are used alone or in combination of two or more.

From the reaction mixture treated in the manner described above,
The desired bromine compound is recovered by a method known per se, for example, by precipitation with a poor solvent.

Further, according to the present invention, a bromine compound represented by the following formula (2) is used as a main component, and a bromine compound represented by the following formula (2) is represented by the following formula (5) based on 1 mol of the bromine compound represented by the following formula (2). A bromine compound is provided, wherein the content of the hydroxybromine compound is 0.02 mol or less.

[0043]

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(In the formula, Ar ¹ and Ar ² may be the same or different and represent an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms. The hydrogen group may be substituted with at least one halogen atom, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single atom. Represents a bond, R
³ and R ⁴ may be the same or different, and represent a hydrocarbon group having 2 to 11 carbon atoms, and this hydrocarbon group is added with a bromine atom. )

[0045]

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(Wherein Ar ¹ , Ar ² and Y have the same meanings as defined in the above formula (2). R ⁶ and R ⁷ are the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms.) p and q are each an integer of 0 to 10, (p + q) is 1 or more, preferably an integer of 2 to 10, s and t are each an integer of 0 to 5, (s
+ T) represents an integer of 1 or more, preferably 1 to 5. )

The bromine compound of the present invention contains the bromine compound represented by the formula (2) as a main component, and preferably contains the bromine compound represented by the formula (2) in an amount of 80% or more, more preferably 85% or more, and particularly preferably. It is a bromine compound containing 90% or more. Ar ¹ and Ar ² in the formula (2) may be the same or different and each have an aromatic hydrocarbon group having 5 to 16 carbon atoms, preferably 6 to 12 carbon atoms, or 5 to 12 carbon atoms.
Preferably, it is a saturated alicyclic hydrocarbon group having 6 to 10 carbon atoms. It is industrially advantageous that Ar ¹ and Ar ² are the same and are aromatic hydrocarbon groups. Specific examples of Ar ¹ and Ar ² include 1,4-phenylene group, 1,4-methylphenylene group, 1,4-dimethylphenylene group, 2,6-
A naphthylene group and a 2,7-naphthylene group;
A 4-phenylene group is preferred.

In these Ar ¹ and Ar ² , the carbon atom forming the hydrocarbon may be substituted with a halogen atom. Particularly, when used as a flame retardant, a halogen atom, especially a bromine atom Is preferably substituted. The number of halogen atoms substituted with each of Ar ¹ and Ar ² is ¹ to 6 with respect to Ar ¹ (or Ar ² ),
Preferably 2 to 4 are advantageous.

In the above formula (2), Y is a group or a bond connecting Ar ¹ and Ar ² and has 1 to 6 carbon atoms.
It is preferably selected from a saturated hydrocarbon group having 1 to 3 carbon atoms; a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, or a single bond. Desirable Y is a methylene group, an isopropylidene group, a cyclohexylidene group, a sulfone group, a sulfide group, a ketone group or a single bond.

In the above formula (2), R ³ and R ⁴ may be the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms, preferably 2 to 5 carbon atoms. An atom has been added. Specific examples of the hydrocarbon group include an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group, and preferably an ethyl group and a propyl group.

As the bromine compound represented by the formula (2), specifically, 2,2-bis [3,5-dibromo-4]
-(2,3-dibromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3
-Dibromo-2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] methane, bis [3,5
-Dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane, [3,3 ', 5,5'
-Tetrabromo-4,4 '-(2,3-dibromopropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4 '-(1,2-dibromoethyloxy)] biphenyl, Bis [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] sulfone and bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] sulfone, among which 2,2 -Bis [3,5-
Dibromo-4- (2,3-dibromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl] propane, bis [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane,
[3,3 ', 5,5'-tetrabromo-4,4'-
(2,3-dibromopropyloxy)] biphenyl and [3,3 ', 5,5'-tetrabromo-4,4'-
(1,2-dibromoethyloxy)] biphenyl is preferred, and 2,2-bis [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3-
Dibromo-2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] methane and bis [3
5-Dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane is more preferred, and in particular, 2,2-bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] propane is preferably used.

In the bromine compound of the present invention, the content of the hydroxy compound represented by the formula (5) is 0.02 mol or less per 1 mol of the bromine compound represented by the formula (2), and -0.02 mol is preferable, 0.0001-0.015 mol is more preferable,
0.0001 to 0.01 mol is more preferable. When the content of the hydroxy compound represented by the formula (5) exceeds 0.02 mol with respect to 1 mol of the bromine compound represented by the formula (2), the thermal stability of the bromine compound of the present invention is preferably reduced. Absent.

The content (mole) of the hydroxy compound represented by the formula (5) relative to 1 mol of the bromine compound represented by the formula (2) was determined to be 280 n by high performance liquid chromatography.
The peak area of the component of the bromine compound represented by the formula (2) obtained from the same chromatography and the peak area of each component of the hydroxy compound represented by the formula (5) It is determined by calculating the sum of the peak areas and calculating the area ratio. Here, since the relative sensitivities of the bromine compound represented by the formula (2) and each component of the hydroxy compound represented by the formula (5) are close to each other, the area ratio can be defined as a molar ratio. Also,
The position of the peak of each component of the hydroxy compound represented by the formula (5) is a peak that increases when the concentration of water is increased during the bromination reaction, and is the peak of the bromine compound represented by the formula (2). It appears at a more polar position.

The hydroxy compound represented by the formula (5) reacts the compound having an aliphatic unsaturated bond represented by the above formula (1) with bromine to synthesize a bromine compound represented by the formula (2). In this case, the solution of the compound having an aliphatic unsaturated bond, bromine or a bromine solution and an active intermediate formed by a reaction between water and bromine present in a reaction solution substantially consisting of a compound having a hydroxyl group, It is a by-product formed by reacting with a compound having an aliphatic unsaturated bond.

Here, the hydroxy compound represented by the formula (5) is an impurity derived from water by-produced in accordance with the compound having an aliphatic unsaturated bond to be used,
Specifically, 2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-hydroxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl]
-2- [3,5-dibromo-4- (2-bromo-3-hydroxypropyloxy) phenyl] propane, 2,2
-Bis [3,5-dibromo-4- (2-hydroxy-3
-Bromopropyloxy) phenyl] propane, 2.2
-Bis [3,5-dibromo-4- (2-bromo-3-hydroxypropyloxy) phenyl] propane, 2-
[3,5-dibromo-4- (2-hydroxy-3-bromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2-bromo-3-hydroxypropyloxy) phenyl] propane;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-Hydroxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy) -4'-
(2-bromo-3-hydroxypropyloxy) {diphenyl] sulfone, bis [3,5-dibromo-4-
(2-hydroxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2-
Bromo-3-hydroxypropyloxy) phenyl] sulfone, [{3,3 ′, 5,5′-tetrabromo-4
-(2-hydroxy-3-bromopropyloxy)-
4 '-(2-bromo-3-hydroxypropyloxy) {diphenyl] sulfone;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-hydroxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-
4- (2,3-dibromopropyloxy) phenyl]-
1- [3,5-dibromo-4- (2-bromo-3-hydroxypropyloxy) phenyl] methane, bis [3
5-dibromo-4- (2-hydroxy-3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-bromo-3-hydroxypropyloxy) phenyl] methane, 1- [3 , 5-dibromo-4-
(2-hydroxy-3-bromopropyloxy) phenyl] -1- [3,5-dibromo-4- (2-bromo-3
-Hydroxypropyloxy) phenyl] methane;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
Hydroxy-3-bromopropyloxyoxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4-
(2,3-dibromopropyloxy) -4 '-(2-bromo-3-hydroxypropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-(2
-Hydroxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'-
(2-bromo-3-hydroxypropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4-
(2-hydroxy-3-bromopropyloxy) -4 '
-(2-bromo-3-hydroxypropyloxy)] biphenyl.

The bromine compound of the present invention can be obtained by the above-described method for producing a bromine compound of the present invention, and the bromine compound can contain a compound represented by the following formula (7).

[0060]

Embedded image

(Wherein Ar ¹ , Ar ² , Y, R ⁶ , R ⁷ , p and q have the same meanings as defined in the above formula (5). R ⁸ and R ⁹ are the same or different, 1-6
Wherein y and z each represent an integer of 0 to 5, and (y + z) represents an integer of 1 or more, preferably 1 to 5. )

As described above, in the compound represented by the formula (7), the active intermediate formed by the reaction of the compound having a hydroxyl group represented by the formula (3) with bromine has the above-mentioned aliphatic unsaturated bond. It is a by-product formed by reacting with the aliphatic unsaturated group of the compound, and the by-product does not adversely affect the thermal stability of the bromine compound. The content of the compound represented by the formula (7) is preferably 0.01 to 0.2 mol, more preferably 0.01 to 0.15 mol, per 1 mol of the bromine compound represented by the formula (2). Preferably
0.01 to 0.1 mol is more preferable, and 0.01 to 0.1 mol.
0.05 mol is particularly preferred. When the content of the compound represented by the formula (7) is the bromine compound 1 represented by the formula (2),
When the amount is 0.2 mol or less with respect to the mol, the flame retardancy of the resin composition containing the bromine compound as a flame retardant in the resin is not adversely affected.

The content (mol) of the compound represented by the formula (7) with respect to 1 mol of the bromine compound represented by the formula (2) can be measured by a method of detecting absorption at 280 nm by high performance liquid chromatography. Calculating the sum of the peak areas of the components of the bromine compound represented by the formula (2) obtained from the same chromatography and the peak areas of the components of the compound represented by the formula (7), and calculating the area ratio thereof. Required by Here, since the relative sensitivities of the bromine compound represented by the formula (2) and each component of the compound represented by the formula (7) are close to each other, the area ratio can be defined as a molar ratio. The position of the peak of each component of the compound represented by the formula (7) is a peak that appears when a compound having a hydroxyl group represented by the formula (3) is added during the bromination reaction.

Here, the compound represented by the formula (7) includes a compound having an aliphatic unsaturated bond and a hydroxyl group-containing compound corresponding to the compound having a hydroxyl group represented by the formula (3). And specifically, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2-methoxy -3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4
-(2,3-dibromopropyloxy) phenyl] -2
-[3,5-dibromo-4- (2-bromo-3-methoxypropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-methoxy-3-bromopropyloxy) Phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-bromo-3-methoxypropyloxy) phenyl] propane, 2- [3,5-
Dibromo-4- (2-methoxy-3-bromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2
-Bromo-3-methoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-ethoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-
4- (2,3-dibromopropyloxy) phenyl]-
2- [3,5-dibromo-4- (2-bromo-3-ethoxypropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-ethoxy-3-bromopropyloxy) ) Phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-bromo-3-ethoxypropyloxy) phenyl] propane, 2- [3,5-
Dibromo-4- (2-ethoxy-3-bromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2
-Bromo-3-ethoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-i-propoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5 -Dibromo-4- (2-bromo-3
-I-propoxypropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-i-
Propoxy-3-bromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-
Bromo-3-i-propoxypropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2-i
-Propoxy-3-bromopropyloxy) phenyl]
-2- [3,5-dibromo-4- (2-bromo-3-i
-Propoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-n-propoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5 -Dibromo-4- (2-bromo-3
-N-propoxypropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-n-
Propoxy-3-bromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-
Bromo-3-n-propoxypropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2-n
-Propoxy-3-bromopropyloxy) phenyl]
-2- [3,5-dibromo-4- (2-bromo-3-n
-Propoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-tert-butoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-
Dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2-bromo-3-tert-butoxypropyloxy) phenyl]
Propane, 2,2-bis [3,5-dibromo-4- (2
-Tert-butoxy-3-bromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (2-bromo-3-tert-butoxypropyloxy) phenyl] propane, 2- [3,5-dibromo-
4- (2-tert-butoxy-3-bromopropyloxy) phenyl] -2- [3,5-dibromo-4- (2
-Bromo-3-tert-butoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5 -Dibromo-4- (2-bromo-3
-I-butoxypropyloxy) phenyl] propane,
2,2-bis [3,5-dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-bromo- 3-i-butoxypropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] -2-
[3,5-dibromo-4- (2-bromo-3-i-butoxypropyloxy) phenyl] propane;

2- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -2- [3,5-
Dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3,5 -Dibromo-4- (2-bromo-3
-N-butoxypropyloxy) phenyl] propane,
2,2-bis [3,5-dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2-bromo- 3-n-butoxypropyloxy) phenyl] propane, 2- [3,5-dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] -2-
[3,5-dibromo-4- (2-bromo-3-n-butoxypropyloxy) phenyl] propane;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-Methoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy) -4'-
(2-bromo-3-methoxypropyloxy)｝ diphenyl] sulfone, bis [3,5-dibromo-4- (2
-Methoxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2-bromo-3-methoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'- Tetrabromo-4- (2
-Methoxy-3-bromopropyloxy) -4 '-(2
-Bromo-3-methoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-Ethoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy) -4'-
(2-bromo-3-ethoxypropyloxy)｝ diphenyl] sulfone, bis [3,5-dibromo-4- (2
-Ethoxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2-bromo-3-ethoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'- Tetrabromo-4- (2
-Ethoxy-3-bromopropyloxy) -4 '-(2
-Bromo-3-ethoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-I-propoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy)-
4 '-(2-bromo-3-i-propoxypropyloxy)｝ diphenyl] sulfone, bis [3,5-dibromo-4- (2-i-propoxy-3-bromopropyloxy) phenyl] sulfone, bis [ 3,5-dibromo-4- (2-bromo-3-i-propoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'-
Tetrabromo-4- (2-i-propoxy-3-bromopropyloxy) -4 '-(2-bromo-3-i-propoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-N-propoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy)-
4 '-(2-bromo-3-n-propoxypropyloxy)｝ diphenyl] sulfone, bis [3,5-dibromo-4- (2-n-propoxy-3-bromopropyloxy) phenyl] sulfone, bis [ 3,5-dibromo-4- (2-bromo-3-n-propoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'-
Tetrabromo-4- (2-n-propoxy-3-bromopropyloxy) -4 '-(2-bromo-3-n-propoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-Tert-butoxy-3-bromopropyloxy)}
Diphenyl] sulfone, [{3,3 ′, 5,5′-tetrabromo-4- (2,3-dibromopropyloxy)
-4 '-(2-bromo-3-tert-butoxypropyloxy) {diphenyl] sulfone, bis [3,5-
Dibromo-4- (2-tert-butoxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5
-Dibromo-4- (2-bromo-3-tert-butoxypropyloxy) phenyl] sulfone, [{3,
3 ', 5,5'-Tetrabromo-4- (2-tert-
Butoxy-3-bromopropyloxy) -4 '-(2-
Bromo-3-tert-butoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-I-butoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy) -4'
-(2-Bromo-3-i-butoxypropyloxy)}
Diphenyl] sulfone, bis [3,5-dibromo-4]
-(2-i-butoxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4-
(2-Bromo-3-i-butoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2-i-butoxy-3-bromopropyloxy) -4'-] (2-bromo-3-i-butoxypropyloxy) {diphenyl] sulfone;

[{3,3 ', 5,5'-tetrabromo-
4- (2,3-dibromopropyloxy) -4 '-(2
-N-butoxy-3-bromopropyloxy) diphenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2,3-dibromopropyloxy) -4'
-(2-Bromo-3-n-butoxypropyloxy)}
Diphenyl] sulfone, bis [3,5-dibromo-4]
-(2-n-butoxy-3-bromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4-
(2-Bromo-3-n-butoxypropyloxy) phenyl] sulfone, [{3,3 ', 5,5'-tetrabromo-4- (2-n-butoxy-3-bromopropyloxy) -4'- (2-bromo-3-n-butoxypropyloxy) {diphenyl] sulfone;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-methoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4
-(2,3-dibromopropyloxy) phenyl] -1
-[3,5-dibromo-4- (2-bromo-3-methoxypropyloxy) phenyl] methane, bis [3,5-
Dibromo-4- (2-methoxy-3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4
-(2-bromo-3-methoxypropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2-methoxy-3-bromopropyloxy) phenyl] -1-
[3,5-dibromo-4- (2-bromo-3-methoxypropyloxy) phenyl] methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-ethoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4
-(2,3-dibromopropyloxy) phenyl] -1
-[3,5-dibromo-4- (2-bromo-3-ethoxypropyloxy) phenyl] methane, bis [3,5-
Dibromo-4- (2-ethoxy-3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4
-(2-bromo-3-ethoxypropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2-ethoxy-3-bromopropyloxy) phenyl] -1-
[3,5-dibromo-4- (2-bromo-3-ethoxypropyloxy) phenyl] methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-i-propoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -1- [3,5 -Dibromo-4- (2-bromo-3
-I-propoxypropyloxy) phenyl] methane,
Bis [3,5-dibromo-4- (2-i-propoxy-
3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-bromo-3-i-propoxypropyloxy) phenyl] methane, 1- [3
5-dibromo-4- (2-i-propoxy-3-bromopropyloxy) phenyl] -1- [3,5-dibromo-4- (2-bromo-3-i-propoxypropyloxy) phenyl] methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-n-propoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -1- [3,5 -Dibromo-4- (2-bromo-3
-N-propoxypropyloxy) phenyl] methane,
Bis [3,5-dibromo-4- (2-n-propoxy-
3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-bromo-3-n-propoxypropyloxy) phenyl] methane, 1- [3
5-dibromo-4- (2-n-propoxy-3-bromopropyloxy) phenyl] -1- [3,5-dibromo-4- (2-bromo-3-n-propoxypropyloxy) phenyl] methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-tert-butoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -1- [3,5 -Dibromo-4- (2-bromo-
3-tert-butoxypropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-tert-
Butoxy-3-bromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-bromo-3-
tert-butoxypropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2-tert-butoxy-3-bromopropyloxy) phenyl] -1-
[3,5-dibromo-4- (2-bromo-3-tert
-Butoxypropyloxy) phenyl] methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl]
-1- [3,5-dibromo-4- (2-bromo-3-i
-Butoxypropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] methane, bis [3,5
-Dibromo-4- (2-bromo-3-i-butoxypropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2-i-butoxy-3-bromopropyloxy) phenyl] -1 -[3,5-dibromo-4- (2-
Bromo-3-i-butoxypropyloxy) phenyl]
methane;

1- [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] -1- [3,5-
Dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl]
-1- [3,5-dibromo-4- (2-bromo-3-n
-Butoxypropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] methane, bis [3,5
-Dibromo-4- (2-bromo-3-n-butoxypropyloxy) phenyl] methane, 1- [3,5-dibromo-4- (2-n-butoxy-3-bromopropyloxy) phenyl] -1 -[3,5-dibromo-4- (2-
Bromo-3-n-butoxypropyloxy) phenyl]
methane;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
Methoxy-3-bromopropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4- (2,3-
Dibromopropyloxy) -4 '-(2-bromo-3-
Methoxypropyloxy)] biphenyl, [3,3 ′,
5,5'-tetrabromo-4,4 '-(2-methoxy-
3-bromopropyloxy)] biphenyl, [3,
3 ', 5,5'-tetrabromo-4,4'-(2-bromo-3-methoxypropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4- (2-methoxy-3-bromopropyloxy) -4'-(2-bromo-3-methoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
Ethoxy-3-bromopropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4- (2,3-
Dibromopropyloxy) -4 '-(2-bromo-3-
Ethoxypropyloxy)] biphenyl, [3,3 ',
5,5'-tetrabromo-4,4 '-(2-ethoxy-
3-bromopropyloxy)] biphenyl, [3,
3 ', 5,5'-tetrabromo-4,4'-(2-bromo-3-ethoxypropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4- (2-ethoxy-3-bromopropyloxy) -4'-(2-bromo-3-ethoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
i-propoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4-
(2,3-dibromopropyloxy) -4 '-(2-bromo-3-i-propoxypropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4'-
(2-i-propoxy-3-bromopropyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-
4,4 '-(2-bromo-3-i-propoxypropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4- (2-i-propoxy-3-bromopropyloxy)- 4 '-(2-bromo-3-i-propoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
n-propoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4-
(2,3-dibromopropyloxy) -4 '-(2-bromo-3-n-propoxypropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4'-
(2-n-propoxy-3-bromopropyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-
4,4 '-(2-bromo-3-n-propoxypropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4- (2-n-propoxy-3-bromopropyloxy)- 4 '-(2-bromo-3-n-propoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
tert-butoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4-
(2,3-dibromopropyloxy) -4 '-(2-bromo-3-tert-butoxypropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,
4 '-(2-tert-butoxy-3-bromopropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4 '-(2-bromo-3-tert-butoxypropyloxy) ] Biphenyl, [3,3 ', 5,
5'-tetrabromo-4- (2-tert-butoxy-
3-bromopropyloxy) -4 '-(2-bromo-3
-Tert-butoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
i-butoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4- (2,
3-dibromopropyloxy) -4 '-(2-bromo-
3-i-butoxypropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-(2
-I-butoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'
-(2-Bromo-3-i-butoxypropyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-4
-(2-i-butoxy-3-bromopropyloxy)-
4 '-(2-bromo-3-i-butoxypropyloxy)] biphenyl;

[3,3 ', 5,5'-tetrabromo-4
-(2,3-dibromopropyloxy) -4 '-(2-
n-butoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4- (2,
3-dibromopropyloxy) -4 '-(2-bromo-
3-n-butoxypropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-(2
-N-butoxy-3-bromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'
-(2-Bromo-3-n-butoxypropyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-4
-(2-n-butoxy-3-bromopropyloxy)-
4 '-(2-bromo-3-n-butoxypropyloxy)] biphenyl and the like.

The bromine compound in the present invention is useful as a stabilizer for γ-ray resistance and a flame retardant, and particularly, a polyolefin resin such as a polyethylene resin or a polypropylene resin,
It is suitable as a flame retardant for polystyrene resins such as BS resin, polystyrene resin, and rubber-modified polystyrene (HIPS) resin.

Further, the bromine compound of the present invention can be identified by a usual analysis technique, for example, analysis of ¹ H-NMR spectrum and IR spectrum.

[0094]

The present invention will be described below in detail with reference to examples. The analysis of purity, impurities derived from water, impurities derived from the hydroxyl group-containing compound, analysis of water content, and measurement of the inclination angle were performed according to the following methods. The hydroxyl group-containing compound used in the examples was purified by distillation in advance, added with molecular sieve 4A, and dehydrated.

(1) Purity of bromine compounds, impurities derived from water, impurities derived from hydroxyl group-containing compounds Purity of bromine compounds, impurities derived from water, and impurities derived from hydroxyl group-containing compounds were measured by high performance liquid chromatography (Shimadzu). 280 by SCL-6B manufactured by MFG.
The measurement was performed by a method of detecting the absorption in nm. As for the purity of the bromine compound, the peak area ratio of the bromine compound to the sum of the peak areas of the respective components obtained from the chromatography was defined as 100. In addition, for the measurement of impurities derived from water and impurities derived from the hydroxyl group-containing compound, the peak area of the bromine compound obtained by this chromatography was obtained, and the sum of the peak areas of the respective components of the water-derived impurity and the hydroxyl group content were determined. The sum of the peak areas of the respective components of the impurities derived from the compound was determined, and the content (mol) relative to 1 mol of each bromine compound was calculated.

(2) Analysis of Moisture Content Coulometric titration moisture meter (CA-06 manufactured by Mitsubishi Chemical Corporation)
) And by the Karl Fischer method.

(3) Inclination angle (after heating at 70 ° C. for 4 hours) A 0.5 g sample was placed in a glass petri dish (Pyrex glass manufactured by Iwaki Glass Co., Ltd .; center line average roughness of the bottom was 0.1 μm).
And placed at 70 ° C for 4 hours using a hot air circulation dryer.
After heating for an hour, the petri dish was taken out and cooled to room temperature. Place this Petri dish on a horizontal surface, lift and tilt the other side while one end is in contact with the horizontal surface, and when the solid sample in the Petri dish slides, the inclination angle of the Petri dish with respect to the horizontal surface viewed from the side Was measured with a protractor (see FIG. 1). This inclination angle means the degree of coagulation of the solid due to the heat treatment, and if the inclination angle is greater than 70 °,
This means that the sample has insufficient thermal stability and is susceptible to blocking.

Example 1 A 1 L glass reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was placed
135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane
And methylene chloride 230 dehydrated with synthetic zeolite
g was added and dissolved. Further, 0.36 g (0.0113 mol) of methanol was added to this solution (the number of hydroxyl groups was 2.6 per 100 aliphatic unsaturated groups). The water content in this solution was 200 ppm (aliphatic unsaturated group 10
The number of water molecules per 0 is 0.94). The solution was then cooled to about 2 ° C. and, with stirring, 72.7 g (0.4
55 mol) was dropped from the dropping funnel over 60 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 16 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, excess bromine in the reaction solution was reduced with 50 g of a 15% by weight aqueous sodium bisulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90% of the methylene chloride was evaporated and removed from the methylene chloride layer, and 500 mL of methanol was added thereto.
The reaction product was precipitated by addition, and the precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
The product was dried under reduced pressure at 5 mmHg for 3 hours at 19 ° C.
g was obtained (yield 97.0%).

When the obtained product was analyzed by ¹ H-NMR, the signal derived from —CHBr— was found to be 4.51 to 4.53 ppm, and the —CH ₂ Br was found to be 3.94 to 4.09 ppm.
Originated signals were observed. Further, from FT-IR analysis, it was confirmed that -O-CH ₂ -absorption was observed and no allyl group absorption was observed. From the above analysis results, the product was found to be mainly 2,2-bis {3,5-dibromo-4-
(2,3-Dibromopropyloxy) phenyl} propane was confirmed. This bromine compound has a purity of 9
5.1%, 2,2-bis {3,5-dibromo-4
The impurity derived from water is 0.004 to 1 mol of-(2,3-dibromopropyloxy) phenyl} propane.
The impurities derived from mol and methanol were 0.015 mol. The inclination angle of the bromine compound was 44 °.

[Example 2] In Example 1, 0.36 g of ethanol (0.00783 m
ol, number of hydroxyl groups per 100 aliphatic unsaturated groups 1.8
), Except that 2,2-bis @ 3,5-dibromo-4- (2,3
(Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 95.3%, and the amount of impurities derived from water is 0.1% based on 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. 004 moles and 0.013 moles of impurities derived from ethanol.

Example 3 In Example 1, 2.33 g (0.038 g) of i-propanol was used instead of methanol.
8 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups 9.
0), and the same method as in Example 1 was carried out except that the initial temperature of the reaction solution was 25 ° C. At the end of the bromine addition, the temperature of the reaction solution was 36 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction, and treated in the same manner as in Example 1 to obtain mainly 2,2-bis @ 3,5-dibromo-4- (2,3- Dibromopropyloxy) phenyl @ propane was obtained. This bromine compound has a purity of 95.0% and 2,2-bis @ 3,5-dibromo-4.
The impurity derived from water is 0.003 to 1 mol of-(2,3-dibromopropyloxy) phenyl @ propane.
0.037 mol, impurities derived from i-propanol
Mole.

Example 4 In Example 3, 1.13 g (0.0%) of n-butanol was used instead of i-propanol.
15 mol, a method similar to that of Example 3 was carried out, except that the number of hydroxyl groups per 100 aliphatic unsaturated groups was 3.5), and 2,2-bis @ 3,5-dibromo-4- was used.
(2,3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 94.9%, 2,2-
With respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane, impurities derived from water are 0.003 mol and impurities derived from n-butanol are 0.021 mol. Mole.

Example 5 The glass reaction vessel used in Example 1 was charged with 2,2-bis {(3,5-dibromo-4-
135 g of allyloxy) phenyl @ propane (0.21
6 mol) and 230 g of methylene chloride. Also, 0.72 g of ethanol (0.
(The number of hydroxyl groups is 3.6 per 100 aliphatic unsaturated groups). The water content in this solution is 500
ppm (number of water molecules per 100 aliphatically unsaturated groups: 2.4). Next, the solution was cooled to about 2 ° C., and while stirring, 72.7 g (0.455 mol) of bromine was added to 60
The mixture was dropped from the dropping funnel over a period of minutes. At the end of the dropwise addition, the temperature of the reaction solution was 16 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 1 to obtain mainly 2,2-bis {3,5-dibromo-
4- (2,3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 94.9%, 2,
2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole,
The impurity derived from water was 0.005 mol, and the impurity derived from ethanol was 0.016 mol. The inclination angle of the bromine compound was 45 °.

[Example 6] In Example 1, the dropping time of bromine was set to 120 minutes, and after completion of the dropping, the reaction solution was continuously stirred for 30 minutes. During the bromination reaction, the temperature of the reaction solution was kept at 20 minutes.
Except for cooling so as to maintain the temperature, the same method as in Example 1 was carried out, and mainly 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} was used.
I got propane. This bromine compound has a purity of 95.2%,
For 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane, 0.003 mol of impurities derived from water and 0 mol of impurities derived from methanol. Was 0.015 mol.

[Example 7] In Example 1, 0.72 g of ethanol (0.016 mol,
Using 230 g of methylene chloride as 615 g (water content in this solution is 200 ppm, the number of water molecules per 100 aliphatic unsaturated groups is 1.9), using the number of hydroxyl groups per 100 aliphatic unsaturated groups (3.6). ), The reaction temperature was set to 39 to 41 ° C, and 80.0 g (0.5
01 mol) was added dropwise in about 5 minutes. After the end of bromine dripping,
The reaction solution was continuously stirred for 60 minutes to complete the bromine addition reaction. This reaction solution was treated in the same manner as in Example 1,
Mainly 2,2-bis {3,5-dibromo-4- (2,
3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 96.1%, and the amount of impurities derived from water is 0.1 mol per mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The amount of impurities derived from 003 mol and methanol was 0.016 mol. The inclination angle of the bromine compound was 41 °.

Example 8 The glass reaction vessel used in Example 1 was charged with 2,2-bis {(3,5-dibromo-4-
Isobutenyloxy) phenyl @ propane 135 g
(0.207 mol) and 230 g of methylene chloride dehydrated with synthetic zeolite were added and dissolved. In this solution, 0.36 g of methanol (0.0113 mol
l) was added (2.7 hydroxyl groups per 100 aliphatic unsaturated groups). The water content in this solution was 200 ppm (the number of water molecules was 0.98 per 100 aliphatic unsaturated groups).
Individual). Next, this solution was cooled to about 2 ° C., and 72.0 g (0.419 mol) of bromine was dropped from the dropping funnel over 60 minutes while stirring. At the end of the dropwise addition, the temperature of the reaction solution was 16 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 1 to obtain mainly 2,2-bis {3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl｝ propane was obtained. This bromine compound has a purity of 9
4.9%, 2,2-bis {3,5-dibromo-4-
With respect to 1 mol of (2,3-dibromo-2-methylpropyloxy) phenyl} propane, 0.003 mol of impurities derived from water and 0.03 mol of impurities derived from methanol were used.
It was 19 moles.

Example 9 The glass reaction vessel used in Example 1 was charged with 2,2-bis {(3,5-dibromo-4-
135 g of allyloxy) phenyl @ sulfone (0.2 g
09 mol) and 230 g of methylene chloride. In this solution, 1.54 g of ethanol (0.
(0335 mol) (number of hydroxyl groups per 100 aliphatic unsaturated groups: 8.0). The water content in this solution is 500
ppm (number of water molecules per 100 aliphatically unsaturated groups: 2.4). Next, the solution was cooled to about 2 ° C., and 80.0 g (0.501 mol) of bromine was added to the solution while stirring.
The mixture was dropped from the dropping funnel over a period of minutes. At the end of the dropwise addition, the temperature of the reaction solution was 16 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 1 to obtain mainly 2,2-bis {3,5-dibromo-
4- (2,3-Dibromopropyloxy) phenyl} sulfone was obtained. This bromine compound has a purity of 93.7%,
For 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone, 0.005 mol of impurities derived from water and 0 mol of impurities derived from ethanol. 0.040 mol.

Example 10 The glass reaction vessel used in Example 1 was charged with 135 g of bis {(3,5-dibromo-4-allyloxy) phenyl} methane (0.227 mol).
l) and chloroform 2 dehydrated with synthetic zeolite
30 g was added and dissolved. 2.33 g (0.0388 mol) of n-propanol was added to this solution (8.5 hydroxyl groups per 100 aliphatic unsaturated groups).
The water content in this solution was 200 ppm (0.90 water molecules per 100 aliphatic unsaturated groups). Next, the solution was set at 25 ° C.
g (0.501 mol) was dropped from the dropping funnel over 100 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 35 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes.
The bromine addition reaction was completed.

Next, this reaction solution was treated in the same manner as in Example 1 to obtain mainly 2,2-bis {3,5-dibromo-
4- (2,3-Dibromopropyloxy) phenyl} methane was obtained. This bromine compound has a purity of 94.5%,
For 1 mol of -bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane, 0.003 mol of impurities derived from water and 0 mol of impurities derived from n-propyl alcohol are used. 0.036 mol.

[Example 11] The glass reaction vessel used in Example 1 was charged with (3,3 ', 5,5'-tetrabromo-
135 g of 4,4'-diallyloxy) biphenyl (0.
232 mol) and 163 g of methylene chloride dehydrated with synthetic zeolite and 70 g of 1,4-dioxane were dissolved therein. In addition, ethanol 1.5
4 g (0.0335 mol) was added (the number of hydroxyl groups per 100 aliphatic unsaturated groups was 7.2). The water content in this solution was 400 ppm (the number of water molecules was 3.6 per 100 aliphatic unsaturated groups). Next, the solution was set at 25 ° C., and 80.0 g of bromine (0.501 mol) was stirred.
l) was dropped from the dropping funnel over 100 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 35 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 1 to obtain mainly {3,3 ', 5,5'-tetrabromo-4,4'-(2,3-dibromopropyloxy)}.
Biphenyl was obtained. This bromine compound has a purity of 94.0%,
{3,3 ', 5,5'-tetrabromo-4,4'-
Impurities derived from water were 0.005 mol, and impurities derived from ethanol were 0.032 mol per 1 mol of (2,3-dibromopropyloxy) biphenyl.

Comparative Example 1 A bromination reaction was carried out in the same manner as in Example 5 except that ethanol was not used, and 2,2-bis @ 3,5-dibromo-4- (2,3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 85.0.
%, 2,2-bis {3,5-dibromo-4- (2,3-
The amount of impurities derived from water was 0.023 mol per 1 mol of dibromopropyloxy) phenyl @ propane. Further, the inclination angle of the bromine compound is 76 °,
It was found that the bromine compound powder easily adhered to each other and had a problem in thermal stability.

Tables 1 to 3 show the results of Examples 1 to 11 and Comparative Example 1. Here, the starting compounds (1) to (5) in the table are: (1) 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (2) 2,2-bis} ( 3,5-dibromo-4-isobutenyloxy) phenyl {propane (3) bis} (3,5-dibromo-4-allyloxy)
Phenyl {sulfone (4) bis} (3,5-dibromo-4-allyloxy)
Phenyl methane (5) (3,3 ', 5,5'-tetrabromo-4,4'
-Diallyloxy) biphenyl, wherein the concentration of the compound having a hydroxyl group indicates the number of hydroxyl groups per 100 unsaturated groups of the compound having an aliphatic unsaturated bond (the number of hydroxyl groups). The number (number) of water molecules per 100 unsaturated groups of the compound having a bond is shown. Further, the impurities (mol) derived from water and the impurities (mol) derived from the compound having a hydroxyl group represent the amount based on 1 mol of the obtained bromine compound.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Table 3]

[0121]

According to the method of the present invention, when a compound having an aliphatic unsaturated bond is reacted with bromine, a compound having a specific hydroxyl group is used, whereby high-purity heat stability is excellent. A bromine compound can be obtained, and such a bromine compound is suitably used as a flame retardant for a resin, and its industrial effect is remarkable.

[Brief description of the drawings]

FIG. 1 is a diagram showing a tilt angle in evaluation of a tilt angle (after heating at 70 ° C. for 4 hours).

[Explanation of symbols]

 1 Glass surface 2 Sample 3 Horizontal surface

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 317/22 C07C 317/22 319/20 319/20 323/17 323/17 323/20 323/20 // C08K 5/06 C08K 5/06 C08L 101/00 C08L 101/00 C09K 21/08 C09K 21/08 (72) Inventor Yasuhiro Shimizu 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Chemicals Limited (72) Inventor Hoshi Haruhisa Mimi 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Chemicals Limited

Claims (10)

[Claims] 1. A solution in which a compound having an aliphatic unsaturated bond represented by the following formula (1) is dissolved in a halogenated aliphatic hydrocarbon solvent, and bromine or a bromine solution are mixed and reacted to obtain the following formula ( In the method for producing a bromine compound represented by 2), a compound having a hydroxyl group represented by the following formula (3) per 100 unsaturated groups is added to the compound having an aliphatic unsaturated bond. The number of hydroxyl groups is 0.5 to
A method for producing a bromine compound, wherein the reaction is carried out by using an amount corresponding to 20 compounds. Embedded image (In the formula, Ar ¹ and Ar ² may be the same or different, and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or 5 carbon atoms.
To 12 saturated alicyclic hydrocarbon groups, which may be substituted with at least one halogen atom, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, or a sulfide group. , A ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single bond, wherein R ¹ and R ² may be the same or different, and have 2 to 11 carbon atoms having at least one aliphatic unsaturated group. It represents a hydrogen group, and ^one of R ¹ and R ² may have a part of the unsaturated group added by a halogen atom. ) (In the formula, Ar ¹ , Ar ² and Y have the same meanings as defined in the above formula (1). R ³ and R ⁴ each represent a case where the unsaturated group in R ¹ and R ² in the above formula (1) is bromine. It means a group saturated by an atom.) (Wherein, R ⁵ represents a u-valent aliphatic group having 1 to 6 carbon atoms, and u represents an integer of 1 to 4). 2. The method according to claim 1, wherein the concentration of water in a solution obtained by dissolving a compound having an aliphatic unsaturated bond in a halogenated aliphatic hydrocarbon solvent, bromine or a bromine solution and a reaction solution substantially consisting of a compound having a hydroxyl group is a fatty acid. 2. The method for producing a bromine compound according to claim 1, wherein the number of water molecules is equal to or less than 10 per 100 unsaturated groups in the compound having a group unsaturated bond. 3. The method for producing a bromine compound according to claim 1, wherein the compound having an aliphatic unsaturated bond is a compound represented by the following formula (4). Embedded image (In the formula, Ar ¹ and Ar ² may be the same or different, and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or 5 carbon atoms.
Represents a saturated alicyclic hydrocarbon group of from 1 to 12, X represents a halogen atom, m and n represent an integer of from 1 to 6, and R ¹ , R ² and Y have the same meanings as defined in the above formula (1). I do. ) 4. A compound having an aliphatic unsaturated bond,
2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3 5-dibromo-4-allyloxy) phenyl {methane, bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane, (3,3 ′, 5,
5'-tetrabromo-4,4'-diallyloxy) biphenyl, (3,3 ', 5,5'-tetrabromo-4,
4'-divinyloxy) biphenyl, bis {(3,5-
The method for producing a bromine compound according to claim 1, which is one kind of compound selected from dibromo-4-allyloxy) phenyl} sulfone and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone. 5. A compound having a hydroxyl group is represented by the formula (3):
In the formula, R ⁵ is a u-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen-containing saturated hydrocarbon group having 1 to 4 carbon atoms or a sulfur-containing saturated hydrocarbon group, and u is an integer of 1 to 2. The method for producing a bromine compound according to claim 1, which is a compound represented by the formula: 6. The compound having a hydroxyl group is methanol,
Ethanol, n-propanol, i-propanol, n
-Butanol, i-butanol, sec-butanol,
The method for producing a bromine compound according to claim 1, which is at least one compound selected from the group consisting of tert-butanol, allyl alcohol, ethylene glycol and diethylene glycol. 7. A bromine compound represented by the following formula (2) as a main component, and a content of the hydroxy bromine compound represented by the following formula (5) per 1 mol of the bromine compound represented by the following formula (2): Is 0.02 mol or less. Embedded image (In the formula, Ar ¹ and Ar ² may be the same or different, and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or 5 carbon atoms.
To 12 saturated alicyclic hydrocarbon groups, which may be substituted with at least one halogen atom, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, or a sulfide group. , A ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single bond, R ³ and R ⁴ may be the same or different, and represent a hydrocarbon group having 2 to 11 carbon atoms, and the hydrocarbon group is A bromine atom is added. ) (Wherein Ar ¹ , Ar ² and Y have the same meanings as defined in the above formula (2). R ⁶ and R ⁷ are the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms. P and q Are each an integer of 0 to 10, (p + q) represents an integer of 1 or more, s and t each represent an integer of 0 to 5, and (s + t) represents an integer of 1 or more.) 8. The bromine according to claim 7, wherein the content of the compound represented by the formula (5) is 0.0001 to 0.02 mol per 1 mol of the bromine compound represented by the formula (2). Compound. 9. A bromine compound represented by the formula (2):
The bromine compound according to claim 7, which is a compound represented by the following formula (6). Embedded image (In the formula, Ar ¹ and Ar ² may be the same or different, and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or 5 carbon atoms.
Represents a saturated alicyclic hydrocarbon group of from 1 to 12, X represents a halogen atom, m and n represent an integer of from 1 to 6, and R ³ , R ⁴ and Y have the same meanings as defined in the above formula (2). I do. ) 10. The bromine compound represented by the formula (2) is 2,2-bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] propane, 2,2
-Bis [3,5-dibromo-4- (2,3-dibromo-
2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl] methane, [3,3 ', 5,5'-tetrabromo-4,4'-(2,3-dibromopropyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-
4,4 '-(1,2-dibromoethyloxy)] biphenyl, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] sulfone and bis [3,5-dibromo-4- The bromine compound according to claim 7, which is a compound selected from (2,3-dibromo-2-methylpropyloxy) phenyl] sulfone.