JP2000072705A - Method for producing bromine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial method for producing a bromine compound having excellent quality as a flame retardant for plastics. A method for producing a bromine compound represented by the following general formula (2) by reacting a compound having an aliphatic unsaturated bond represented by the following general formula (1) with bromine:
The reaction is carried out in the presence of a solvent inert to the reaction, and a substantial amount of the heat of reaction is removed outside the reaction system by the heat of vaporization of the solvent or bromine. (Wherein, Ar ¹ and Ar ² represent an aromatic hydrocarbon group or a saturated alicyclic hydrocarbon group; Y represents a group that binds Ar ¹ and Ar ² ; R ¹ and R ² represent an aliphatic group) R ³ and R ⁴ represent a hydrocarbon group having at least one unsaturated group.
Represents a group in which the unsaturated group in R ¹ and R ² is saturated by a bromine atom, respectively. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a bromine compound by brominating a compound having an aliphatic unsaturated bond. More specifically, the present invention relates to a method for industrially advantageously producing a high-purity bromine compound from a compound having an aliphatic unsaturated bond.

[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. For this reason, it is essential to remove reaction heat from the reaction system, and for that purpose, an operation of cooling the reaction system and adding bromine over a long period of time in a mild state is generally adopted. .

For example, Japanese Patent Publication No. 49-39655 discloses a method for producing β, γ-dibromopropylbenzene, but at a low temperature such that a side reaction does not occur when bromine is added. The reaction is described.

Japanese Patent Application Laid-Open No. 55-111429 discloses that diallyl ether obtained from 2,2-bis-{(4-hydroxy-3,5-dibromo) phenyl} propane and allyl chloride is aromatic. It is disclosed that the bromination is carried out in a halogenated hydrocarbon solvent, but it is described that such bromination is carried out at a temperature of 10 to 30 ° C, particularly 15 to 25 ° C. Specifically, a method of adding bromine under cooling at a temperature of about 20 ° C. is shown.

Japanese Patent Application Laid-Open No. 50-30853 relates to a method for recovering a solid, and in the examples, 2,2-bis (Δ (3,
The reaction of 5-dibromo-4-allyloxy) phenyl} propane with bromine specifically describes a method of dropping bromine at a temperature of 20 ° C. or lower.

In Japanese Patent Application Laid-Open No. 7-173092, as a method for obtaining a 2,3-dibromopropyl compound, specifically, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and For the reaction with bromine, a method in which bromine is added dropwise at a reaction temperature of 10 to 20 ° C. over 1 hour is described.

Further, Japanese Patent Application Laid-Open No. 7-316087 discloses a specific example of 2,2-bis {(3,5-dibromo-
A method is disclosed in which bromine is added dropwise to a methylene chloride solution of 4-allyloxy) phenyl} propane over 1 hour while controlling the reaction temperature at 24 to 27 ° C. by using a cooling tube.

On the other hand, for example, Japanese Patent Publication No. 50-23693 discloses a bis (3,5-dibromo-4) as a specific example.
In the bromination of (allyloxy) phenyl} sulfone, 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 added dropwise to a methylene chloride solution at 39 ° C. or 40 ° C. over 1 hour, and the latter is bromine at 35 to 39 ° C. For 1.5 hours. In each of these methods, the reaction is carried out in a vessel having a cooling pipe.

[0010] The methods described in these patent publications are all small-scale reactions at the laboratory level. In many cases, a flask is used as a reactor, and most of the reactions are performed by cooling the reactor itself. A method of removing heat is employed. Although these publications disclose conditions and means at a laboratory level, they are effective on an industrial scale to effectively remove a large amount of heat of reaction and to obtain a high-purity bromide with a high yield. No specific conditions or means are disclosed.

In order to carry out bromination, particularly polybromination, of a compound having an aliphatic unsaturated bond on an industrial scale, it is necessary to effectively remove large amounts of reaction heat.
Development of means and devices for that purpose is required. If the heat of reaction is not effectively removed, bromine must be supplied gradually, which increases the reaction time, resulting in a decrease in yield and a decrease in purity.

[0012]

In view of the above situation, the present inventors have developed a method for producing a highly pure bromine compound by efficiently reacting a compound having an aliphatic unsaturated bond with bromine on an industrial scale. As a result of intensive research aimed at providing the compound, it has been found that when a compound having an aliphatic unsaturated bond is reacted with bromine in the presence of a solvent inert to the reaction to cause bromination, a substantial heat of bromination reaction is obtained. The present inventors have found that by removing the amount of the bromine compound outside the reaction system by the heat of vaporization of the solvent or bromine, a side reaction does not occur and a high-purity bromine compound can be produced in high yield, and the present invention has been achieved.

[0013]

That is, according to the present invention, a compound having an aliphatic unsaturated bond represented by the following general formula (1) is reacted with bromine to form a compound represented by the following general formula (2). Wherein the reaction is carried out in the presence of a solvent inert to the reaction, and a substantial amount of the heat of reaction is removed from the reaction system by the heat of vaporization of the solvent or bromine. A method for producing a bromine compound is provided. R ¹ —O—Ar ¹ —Y—Ar ² —O—R ² (1) (wherein, Ar ¹ and Ar ² may be the same or different and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and these hydrocarbon groups may be substituted by at least one halogen atom; Y is a saturated hydrocarbon group having 1 to 6 carbon atoms, sulfone A sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single bond; R ¹ and R ² may be the same or different, and have 2 carbon atoms having at least one aliphatic unsaturated group. And R 11 represents a hydrocarbon group of any one of R ¹ and R ² , and ^one of R ¹ and R ² may have a part of the unsaturated group added by a halogen atom.) R ³ —O—Ar ¹ —Y—Ar ^{2 -O-R 4 (2)} ( wherein, Ar ^1, Ar ² and Y are Means the same thing as defined in serial formula (1) .R ³ and R ⁴ are each unsaturated group in R ¹ and R ² in the general formula (1) means a saturated group by a bromine atom. )

Hereinafter, the method for producing a bromine compound according to the present invention will be described more specifically and in detail. The compound having an aliphatic unsaturated bond used in the method of the present invention is
It is represented by the general formula (1). In the general 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-dimethylphenylene, 1,4-methylphenylene, 1,4-dimethylphenylene, 2,6-naphthylene, and 2,7-naphthylene. A 1,4-phenylene group is preferred.

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

In the general formula (1), R ¹ and R ² may be the same or different and each have at least one aliphatic unsaturated group and have 2 to 11 carbon atoms, preferably 2 carbon atoms.
Represents any one of R ^{1 to} R ² , and ^one of R ¹ and R ² may be partially substituted with a halogen atom, preferably a bromine atom, and may be saturated. 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 general 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, and 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 and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane are more preferred, especially 2,2-bis {(3,5-dibromo-4-). Allyloxy) phenyl dipropane is preferably used.

In the method of the present invention, the reaction between the compound having an aliphatic unsaturated bond and bromine is carried out in the presence of a solvent,
The solvent must be inert without adversely affecting the reaction. 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 used not only as a mere solvent for performing the reaction uniformly,
Preferably, it has a function as a solvent for effectively removing the heat of reaction out of the system. Therefore, it is advantageous that the solvent has a normal pressure boiling point in the range of 0 to 100 ° C, preferably 20 to 90 ° C. In particular, when the reaction heat is substantially removed by the heat of vaporization of the solvent, the normal pressure boiling point is 20 ° C. -80 ° C, especially 20-60
A temperature in the range of ° C is desirable.

Examples of such a solvent include halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, diethyl ether, ethyl isopropyl ether, tetrahydrofuran, dioxane and the like. Examples include ether hydrocarbon compounds, aromatic hydrocarbon compounds such as benzene, carbon disulfide, pentane, and the like. Also, bromine can be used as a solvent.

Among these solvents, halogenated hydrocarbons are preferable, and methylene chloride and chloroform are particularly preferably used as the solvent. 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.

These solvents are used with respect to the compound represented by the general formula (1) in an amount of 2 to 2 per unsaturated group in the compound.
It is used in an amount of 1000 molecules, preferably 2.5 to 800 molecules. In the reaction of the present invention, since it is a preferable embodiment to remove a substantial amount of the reaction heat to the outside of the reaction system by the heat of vaporization of the solvent, the solvent is more preferably 3 to 700 molecules, particularly preferably 4 to 600 molecules. It is advantageous to use them in molecular proportions.

The method of the present invention is characterized in that the reaction heat is discharged by the heat of vaporization of the solvent or bromine, so that the solvent or bromine is present in the reaction system in an amount that can provide the heat of vaporization corresponding to the heat of reaction. However, since bromine participates in the reaction, it is reasonable and advantageous to remove the heat of reaction preferably by the heat of vaporization with a solvent.

The amount of bromine used in the method of the present invention may be a sufficient molar ratio to the compound having an aliphatic unsaturated bond in order to obtain a desired bromine compound. Is preferably in the range of 1 to 5 molecules of bromine, more preferably in the range of 1.1 to 3 molecules of bromine per unsaturated group in the compound having

In the method of the present invention, bromine itself 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.

In the method of the present invention, as a specific means, a solution in which a compound having an aliphatic unsaturated bond is dissolved in a solvent inert to bromine is mixed with bromine or a bromine solution to obtain an aliphatic unsaturated bond. A compound having a saturated bond is reacted with bromine. At the time of this bromination reaction, it is an essential condition that a substantial amount of the heat of the bromination reaction is removed by a solvent or the heat of vaporization of bromine. The substantial amount of the heat of reaction means at least 80%, preferably at least 85% of the theoretical calorific value generated by the desired bromination reaction.

The reaction temperature in the bromination reaction of the present invention is as follows:
There is no particular limitation, as described above, as long as the substantial amount of the bromination reaction heat is a temperature at which the bromine or the heat of vaporization of the solvent is removed, and the bromination reaction is not limited to normal pressure, and It can be performed under reduced pressure or reduced pressure. The reaction temperature is preferably at least 0 ° C, more preferably at least 5 ° C. 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 of the present invention can be controlled by operating pressure, depending on the type of solvent (boiling point) and the amount of bromine used. Usually the reaction temperature is 0
A range of 60 ° C., preferably 5 to 55 ° C., particularly preferably 10 to 50 ° C. is advantageous.

In the method of the present invention, during the bromination reaction, a substantial amount of the heat of the bromination reaction is removed by the heat of vaporization of the solvent or bromine, but the vaporized vapor is placed at the top of the reactor. Liquefied by cooling with a condenser
A method of returning to the reaction system again, that is, a method of refluxing, is preferably used because of easy operation. The removal of the heat of reaction by vaporization can also be performed by a method without using a condenser. This method will be described later.

By removing a substantial amount of the heat of reaction for bromination with a solvent or the heat of vaporization of bromine, the resulting bromine compound becomes highly pure. 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 a reaction at a low temperature, but the method of the present invention requires a high purity. Can be obtained. This is considered to be because the compound having an aliphatic unsaturated bond and bromine are uniformly dispersed in the solution due to the stirring effect when the solvent or the bromine is vaporized, and the side reaction is less likely to occur.

In the method of the present invention, the method of mixing a solution in which a compound having an aliphatic unsaturated bond is dissolved in an inert solvent with bromine or a bromine solution is not particularly limited. A method of adding and mixing a solution of a compound having an aliphatic unsaturated bond to a solution of a compound having an aliphatic unsaturated bond to a bromine or bromine solution; Any method of simultaneously adding the solution of the compound having an unsaturated bond to the reactor and mixing the solution can be adopted.

In the method of the present invention, the reaction between the compound having an aliphatic unsaturated bond and bromine is carried out in the presence of a solvent inert to the reaction, and the amount of heat of reaction is controlled by the heat of vaporization of the solvent or bromine. It is necessary to remove the reaction heat generated outside the reaction system. For this reason, it is necessary to employ conditions and means for effectively discharging a large amount of reaction heat as a vapor of the solvent or bromine as the vapor outside the reaction system. desirable. These conditions and means will be described below in detail and in detail. However, the reaction components and the solvent come into uniform contact, the solvent and the bromine are effectively vaporized, and the reaction heat is discharged out of the system. It is desirable that the reaction be carried out smoothly, as a result, the reaction can be completed earlier and a bromine compound having excellent purity can be obtained. For this reason, adoption of a means for sufficiently mixing the reaction mixture in the reaction system gives more preferable results.

Thus, the selection of the above-mentioned solvent and its ratio,
It is industrially advantageous that the ratio of bromine and the reaction temperature are set within the above ranges. It has further been found that the presence of water and the addition of alcohol in the reaction system affect the purity and quality of the bromine compound. These points will be described below.

In the reaction of the present invention, impurities present in the reaction solution are important factors for efficiently performing the bromination reaction of the present invention and for obtaining a high-yield, high-purity bromine compound. . In particular, water present in the reaction solution reacts with bromine to form an active intermediate, and the active intermediate reacts with the aliphatic unsaturated group in a competitive reaction, so that the The presence of water contained in the compound having an unsaturated bond, bromine and the solvent requires careful attention, and basically, the coexistence of water should be avoided. Therefore, the concentration of water is preferably 10 molecules or less, more preferably 0.05 to 10 molecules, and more preferably 0.010 molecules per 100 unsaturated groups of the compound having an aliphatic unsaturated bond.
5 to 5 molecules are more desirable. As the concentration of water increases,
The resulting bromine compound is of low purity, easily adheres to each other, and becomes a solid lacking in storage stability, which is not preferable. The water content is measured by the Karl Fischer method.

The concentration of water in the reaction solution can be reduced to some extent by removing water contained in the compound having an aliphatic unsaturated bond, bromine and the solvent. However, when the reaction is carried out on an industrial scale, it is extremely difficult to avoid mixing of a certain amount of water into the reaction system due to restrictions on equipment and operation. Thus, the present inventors have conducted research on a method that does not significantly affect the handling and use of the obtained bromine compound even when a trace amount of water is present in the reaction system. It has been found that the method of adding a specific alcohol is excellent. The alcohol added to the reaction system is represented by the following general formula (3). R ^5- (OH) _n (3) (wherein, R ⁵ represents an n-valent aliphatic group having 1 to 6 carbon atoms;
n shows the integer of 1-4. )

In the general formula (3), R ⁵ is 1 to 4
Aliphatic group having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms
Or an oxygen-containing saturated hydrocarbon group having 1 to 4 carbon atoms or a sulfur-containing saturated hydrocarbon having 1 to 4 carbon atoms. N is an integer of 1 to 4, preferably 1 or 2. As the alcohol represented by the general formula (3), 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 te
rt-butanol is preferred, especially methanol, ethanol and i-propanol.

Such an alcohol has a number of hydroxyl groups of 0.5 to 20, preferably 0.8 to 1, per 100 unsaturated groups of the compound having an aliphatic unsaturated bond.
8, more preferably 1 to 15, particularly preferably 1 to
An amount equivalent to 10 is used. When the amount of alcohol is less than the amount corresponding to 0.5 hydroxyl groups per 100 unsaturated groups of the compound having an aliphatic unsaturated bond, the compound is formed by the reaction of water and bromine. When the reaction between the active intermediate and the compound having an aliphatic unsaturated bond is facilitated, the thermal stability of the resulting bromine compound is undesirably reduced, and when the amount exceeds 20 equivalents,
An intermediate produced by the reaction of the alcohol and bromine, the amount of by-products produced by reacting with a compound having an aliphatic unsaturated bond increases, the purity of the resulting bromine compound becomes insufficient, It is not preferable because the flame retardancy of a resin composition containing such a bromine compound as a flame retardant in a resin is adversely affected.

In the bromination reaction of the present invention, as described above, the alcohol represented by the general formula (3) is added to a solution obtained by mixing a solution of a compound having an aliphatic unsaturated bond with bromine or a bromine solution. By the presence, the generation of by-products due to moisture is suppressed. However, if the amount of water present in the mixed solution is too large, a large amount of the compound having a hydroxyl group is used in order to suppress a side reaction due to moisture. An intermediate produced by the reaction with bromine produces a large amount of by-products that have reacted with the compound having an aliphatic unsaturated bond, and the purity of the obtained bromine compound becomes insufficient. This will have an adverse effect on the flame retardancy of the resin composition blended with the resin as a flame retardant. 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. As described above, the unsaturated group 1
An amount corresponding to 10 or less water molecules per 00 is preferable, an amount corresponding to 0.05 to 10 is more preferable, and an amount corresponding to 0.05 to 5 water molecules is more preferable.

The process of the present invention uses a batch process as long as a substantial amount of the heat of reaction is discharged as the heat of vaporization of the solvent or bromine, and preferably most of the heat of reaction is discharged out of the reaction system as the heat of vaporization of the solvent. , A semi-batch system or a continuous system. The batch system and the continuous system will be described below for the sake of simplicity, but partial changes and modifications are permissible as long as the essence of the present invention is not impaired. In particular, the semi-batch system is easily adopted by the combination known per se from the description of the batch system and the continuous system.

In the following description, the description of the control of water in the reaction system and the addition of alcohol will be omitted. In particular, when an alcohol is added, it may be added alone, or may be added to a compound having an aliphatic unsaturated bond, bromine or a solvent. Moreover, you may add to these mixtures. In the following description, a compound having an aliphatic unsaturated bond is simply referred to as an “unsaturated compound”.
And the solvent inert to the reaction is simply abbreviated as “solvent”.

(I) Batch system: In a batch system, an unsaturated compound, bromine and a solvent are charged into a reactor in an arbitrary order, the reaction and the heat of reaction are removed in the reactor, and substantially until the reaction is completed. In this method, the reaction mixture is not taken out. This batch system is described in Ia to I below.
-D. Scheme (Ia): This scheme (Ia) is a scheme in which the unsaturated compound, bromine and the solvent are fed separately or simultaneously as a mixture of any combination into the reactor. This method (I-
a) represents a predetermined ratio of an unsaturated compound, bromine and a solvent,
It is desirable to feed the reactor at about the same rate, and the solvent may be added as a solution of the unsaturated compound or as a solution of bromine. When the solvent is added as a solution of an unsaturated compound and / or a solution of bromine, the solvent may be supplementarily added alone, or a part of the solvent may be charged in the reactor in advance.

As described above, in the reaction of the present invention, it is desirable that the unsaturated compound, bromine and the solvent come into contact with each other uniformly and effectively. Therefore, a reactor equipped with a stirrer is used. Further, a reactor in which the solvent and bromine vaporized by the heat of reaction are refluxed into the reaction system by a condenser provided at the top of the reactor is advantageous. The reactor equipped with the stirrer and the condenser is advantageously used in any of the following modes.

Particularly, in order to uniformly contact the unsaturated compound, bromine and the solvent in the reactor, when they are fed to the reactor, they are thoroughly mixed using a flow mixer, especially a static mixer. It is a more preferred embodiment to supply the solution to the reactor.

Method (Ib) This method (Ib) is a method in which an unsaturated compound or a solution thereof is supplied to a reactor filled with bromine or a solution of bromine. In this method (Ib), the solvent is preferably added as a solution of bromine, unsaturated compound or both, but it is also possible to supplement a part of the solvent alone.

In this method (Ib), the bromination reaction can be performed in a short time, and the productivity is improved. Since the bromination reaction itself is almost completed in several tens of seconds, it is usually sufficient that the time from the start of the bromination reaction to the end of the reaction is within several minutes.

A method of adding a solution of an unsaturated compound to bromine or a bromine solution in a reactor in this method (Ib) will be described.
The rate of adding the unsaturated compound is preferably 0.4 to 1000 mmol / sec, more preferably 0.4 to 300 mmol / sec, and still more preferably 0.5 to 500 mol / mol.
A method of adding 100 mmol / sec is adopted.

Method (Ic) This method (Ic) is a method in which an unsaturated compound and bromine are separately supplied into a reactor filled with a solvent in advance. In this scheme (Ic), the unsaturated compound is supplied as a solution in a solvent. Bromine can also be supplied as a solution. In this manner, the proportions of unsaturated compound, bromine and solvent are not substantially different from the ranges described above.

Method (Id) This method (Id) is a method in which bromine or a bromine solution is supplied to a reactor filled with an unsaturated compound or a solution thereof. In this mode (Id), the solvent is preferably added with the unsaturated compound, bromine or both solutions, but it is also possible to supplement a portion alone.

The method of adding bromine or a bromine solution to the solution of the unsaturated compound in the reactor in this method (Id) will be described more specifically. That is, the bromine or the bromine solution has a bromine addition rate of at least 0.4 mmol / sec, preferably at least 0.5 mmol / sec, more preferably at least 1 mmol / mol of the unsaturated compound.
Sec or more, particularly preferably 1.5 mmol / sec or more, and 1000 mmol / sec or less, preferably 30 mmol / sec or less.
0 mmol / sec or less, more preferably 100 mmol / sec.
A method is used in which the addition is carried out at a rate of not more than second, more preferably at most 50 mmol / sec, particularly preferably at most 20 mmol / sec. If the addition rate of bromine or bromine solution is too slow, productivity may decrease, which is not preferable,
If the addition rate is too high, the reaction may not be controlled, which is not preferable.

The product of the rate (mmol / sec) of adding the bromine and the concentration (mol / L) of the solution of the unsaturated compound in the solvent is preferably 0.7 or more per mole of the compound, preferably 0.7 or more. 7 to 200 is more preferable, and 0.7 to 100 is adopted as still more preferable condition. If the value of this product is smaller than the above-mentioned value, the concentration of the unsaturated compound solution will be remarkably reduced, and the production efficiency will be undesirably reduced.

The batch system described above is industrially the system (Ia), the system (Ib) or the system (Ic), particularly from the viewpoint of the quality and purity of the obtained bromine compound. ,
Scheme (Ib) or scheme (Ic) is preferred.

(II) Continuous Method The present inventors have further studied and found that a technique for producing a bromine compound for removing a substantial amount of the reaction heat to the outside of the reaction system by the heat of vaporization of a solvent or bromine is described later. It has been found that a highly compact bromine compound can be efficiently obtained with a very compact and simple reactor by applying the continuous method as described above, and with a short reaction time.

That is, according to the present invention, the compound having an aliphatic unsaturated bond represented by the general formula (1) is reacted with bromine to produce a bromine compound represented by the general formula (2). In the above method, the compound represented by the general formula (1), bromine and a solvent inert to the reaction are continuously supplied to a reactor separately or as a mixture of any combination. For the compound represented by the general formula (1), 1 to 5 per unsaturated group in the compound
A quantity of bromine is supplied as a molecule, and the reaction is performed while removing a substantial amount of heat of reaction in the reactor by the heat of vaporization of the solvent or bromine.The reaction mixture is taken out of the reactor, and then the reaction mixture is subjected to the reaction. A method for continuously producing a bromine compound, comprising recovering the bromine compound represented by the general formula (2).

In the continuous system of the present invention, the compound represented by the general formula (1), bromine, and a solvent inert to the reaction are supplied separately or continuously as a mixture of any combination. At that time, the compound represented by the general formula (1) (unsaturated compound) and bromine react rapidly when they are brought into contact with each other. Therefore, it is necessary to avoid mixing these two in advance and supplying them to the reactor. It is.

In the implementation of the continuous system, the system for supplying the unsaturated compound, bromine and the solvent to the respective reactors is classified into the following (i) to (iii). (I) The solution of the unsaturated compound and the bromine are separately supplied. (Ii) separately providing a solution of the unsaturated compound and a solution of bromine. (Iii) The unsaturated compound, bromine and the solvent are separately supplied.

The above (i) to (iii) are for explaining the combination of the supplying means for the unsaturated compound, bromine and the solvent required for carrying out the continuous system of the present invention. Partial modifications are naturally included in the present invention. When there is another component to be added, the component may be added independently, may be added as a solvent solution, or may be added to a solution of an unsaturated compound or a solution of bromine. Other components to be added include, for example, alcohols represented by the above general formula.

Next, the proportions of the unsaturated compound, bromine and the solvent inert to the reaction which are supplied to the reactor will be described. These proportions do not substantially differ from the above-mentioned proportions. That is, the solvent is used in a ratio of at least 2 molecules, preferably at least 2.5 molecules, more preferably at least 3 molecules, most preferably 4 molecules per unsaturated group per unsaturated compound.

The upper limit is limited from an economic point of view.
Generally, it is desirable that the number of molecules be 1,000 or less, preferably 800 or less, and particularly preferably 700 or less. Most advantageously it is less than 500 molecules. Bromine is advantageously in the range of 1 to 5 molecules, more preferably in the range of 1.1 to 3 molecules, per unsaturated group in the unsaturated compound. Especially 1.2
A range of ~ 3 molecules is industrially advantageous.

In the continuous system of the present invention, in the reaction solution in the reactor, one or more, preferably 1 to 5, more preferably 1 to 5 molecules of bromine per aliphatic unsaturated group in the unsaturated compound. It is imperative that it be kept in the range of .1-3 molecules. It is required that the bromine always maintain the above ratio during the reaction in the reaction solution in order to obtain a high-purity and high-quality bromine compound. There is no particular problem if the bromine ratio is momentarily (on the order of several seconds) smaller than the above range, but the substantial reaction time and the bromine ratio should be maintained in the above ranges. If the proportion of bromine is kept below the above range for a long time, the unsaturated group in the unsaturated compound will cause a side reaction to produce an undesired side reaction product and lower the purity of the target bromine compound. This side reaction is considered to occur mainly when the active intermediate formed by the reaction of water and bromine in the reaction solution reacts with the unsaturated group.

In order to maintain the ratio of bromine in the reaction solution in the continuous system to at least one molecule, preferably at least 1.1 molecule per unsaturated group in the unsaturated compound, it is necessary to supply the unsaturated compound to the reactor. What is necessary is just to always maintain the said supply ratio of a compound and bromine.

The bromination reaction takes place immediately in the reactor, and the generated heat of reaction must be removed by vaporizing the solvent or bromine. A method in which the vaporized solvent or bromine vapor is cooled and liquefied by a condenser or the like provided in the upper part of the reactor and returned into the reaction solution, that is, a method of refluxing is preferably used because the operation is easy. By removing the reaction heat of the bromination with the solvent or the heat of vaporization of the bromine, the resulting bromine compound becomes highly pure.
Simply reacting the unsaturated compound 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 the method of the present invention, a high-purity bromine compound is obtained. be able to. It is considered that the unsaturated compound and bromine are uniformly dispersed in the solution due to the stirring effect of the reflux, and the side reaction is less likely to occur.

The amount of the solution in which the unsaturated compound was dissolved in the solvent was A (L / min), the amount of the bromine or the bromine solution was B (L / min), and the amount of the reaction solution in the reaction tank was C. In the case of (L), the residence time represented by the following formula is 0.1 to 20.
It is desirable to perform the bromination reaction for 0 minute, preferably 0.2 to 100 minutes.

Here, the total amount of the addition amount (L / min) of the solution in which the unsaturated compound is dissolved in the solvent and the addition amount (L / min) of the bromine or the bromine solution are strictly speaking outside the reactor. Although different from the derived amount (L / min) of the derived reaction solution, the amount of bromine added (L / min) is usually smaller than that of the solution (L / min) of the unsaturated compound with respect to bromine. Yes, the volume change due to the reaction is almost negligible. Further, since the amount of the solvent scattered outside the reactor is very small, the addition amount of the solution in which the unsaturated compound is dissolved in the solvent with respect to bromine (L / min) and the addition amount of the bromine or the bromine solution (L / min) And the total amount (L / min) of the reaction solution led out of the reactor.

Recirculating a part of the reaction solution to the reactor is advantageously employed because the reactor can be made more compact and the reaction efficiency is excellent. The method of circulation is not particularly limited, and another pipe dedicated to circulation may be attached to the reactor separately from the outlet of the reaction solution, or a part of the derived reaction solution may be circulated to the reactor. . The circulated reaction solution may be added to the reactor as it is, or may be mixed with a solution of an unsaturated bond compound, bromine or a bromine solution, or a mixed solution thereof, and the resulting mixture may be returned to the reactor. Good.

In the continuous system of the present invention, the above-mentioned circulation method is preferable because the bromination reaction can be performed in a short time and the productivity is improved. Since the bromination reaction itself is almost completed in several tens of seconds, the above-mentioned residence time is sufficient.

The reaction temperature in the bromination reaction of the present invention is as follows:
It is sufficient that the heat of the bromination reaction is a temperature at which the bromine or the heat of vaporization of the solvent is removed, and the bromination reaction is not limited to normal pressure, and can be performed under pressure or under reduced pressure. The reaction temperature is 0 ° C to 60 ° C as described above.
Is preferable. 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.

In carrying out the continuous process of the present invention, the reactor is brought into uniform and effective contact with the unsaturated compound, bromine and the solvent, and a substantial amount of the heat of reaction is discharged out of the reactor by vaporizing the solvent or bromine. It is desirable to use a device equipped with a stirrer to perform the reaction, and a device provided with a condenser at the top for refluxing the vaporized solvent or bromine.

According to the study of the present inventors, in carrying out this continuous mode, the unsaturated compound, bromine and the solvent are brought into uniform contact with each other in the reactor, and the bromination reaction and the solvent or bromine of the heat of reaction are carried out. In order to more effectively remove by vaporization, the unsaturated compound and bromine are desirably mixed and supplied together with at least a part of the solvent in a short period of time immediately before being supplied to the reactor. Was found to be effective.

Mixing of the unsaturated compound and bromine immediately before feeding to the reactor (the solvent may be further mixed)
Should be carried out in a short time and uniformly, so that it is preferably supplied to the reactor as a mixture stream using a flow mixer. The mixing in the flow mixer is the unsaturated compound and bromine, but also some or all of the solvent is mixed together.

The mixed liquid flow in the flow mixer desirably achieves uniform mixing in a short time.
~ 500 cm / sec flow rate, preferably 50-400 cm
Advantageously, a flow rate of / s. The residence time of the mixed liquid flow in the flow mixer is 0.01 to 180.
Seconds, preferably 0.05 to 120 seconds, more preferably 0.1 seconds.
1 to 60 seconds is appropriate. In particular, 0.1 to 20 seconds is recommended.

The flow mixer is not particularly limited as long as it can effectively and uniformly mix the liquid mixed stream in a short time, and a static mixer is particularly preferable. As this static mixer, one having 4 to 20 elements, preferably 5 to 15 elements is advantageously used.

A static mixer is a chemical engineering device commonly known as a mixer or heat exchanger. The static mixer is a mixer commercially available from Kenix Corporation of the United States, which is a tube-type mixer having no driving unit, and in which a rectangular plate called an element is twisted at right and left directions in opposite directions. The object has a built-in structure, and the torsion directions are arranged so that the right and left cross sections thereof cross each other at right angles.

In the continuous system of the present invention, when the unsaturated compound, bromine and the solvent are continuously supplied to the reactor,
Performing these feeds using a flow mixer, especially a static mixer, is extremely effective for completing the bromination reaction in a very short time, suppressing side reactions, and obtaining a high-purity bromine compound. Means.

The mixed solution mixed in the flow mixer is immediately supplied to the reactor. The solution mixed in the flow mixer starts a part of the bromination reaction, but the residence time in the mixer is controlled to be short, so the mixed solution passing through the mixer is immediately discharged to the reactor. . In the reactor, the solution is further stirred so that it is sufficiently mixed. The stirring is preferably performed using a stirrer,
A method of circulating a part of the solution from the inside of the reactor may be used.

The capacity of such a reactor is 3 times the mixer capacity.
Those having a capacity of 0 times or more and 50 times or more are preferable.
The upper limit of the size of such a reactor is not particularly limited, but it is sufficient if it is 200,000 times or less the mixer capacity, and the use of a reactor exceeding 200,000 times is economically undesirable. Such a large-capacity reactor has a function of suppressing the scattering of the solvent and bromine due to boiling by dissipating the reaction heat generated when reacting in the mixer in the reactor, and promoting the stirring and mixing. This has the effect of completing the bromination reaction.

At this time, a method of removing the reaction heat of the bromination by the heat of vaporization of the solvent or bromine can be adopted. In addition, a condenser is attached to the reactor, and the vaporized vapor is cooled, liquefied and re-evaporated. A method of returning to the reaction solution, that is, a method of refluxing is more preferably used because the operation is easy.
In this method, the unsaturated compound and bromine are uniformly dispersed in the solution due to the stirring effect by the reflux, side reactions are less likely to occur, and a high-purity bromine compound is easily obtained, and the reaction temperature is kept constant. However, it is preferably used because the bromination reaction proceeds stably without scattering of a solvent or bromine.

(III) Separation / Recovery of Bromine Compound: The target 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 the residual bromine with a reducing agent, converting bromine to hydrobromic acid once, and then adding an alkaline neutralizing agent is usually adopted. ing.

However, this method requires at least two steps of a reduction treatment and a neutralization treatment, and the operation is complicated and the treatment takes a long time. Moreover, the purity and quality of the bromine compound recovered by this treatment method are not sufficiently satisfactory.

Thus, the present inventors have improved the method for separating and recovering the bromine compound from the reaction mixture by a simple means in a short time, and found that the residual bromine in the reaction mixture was reduced by a specific amount or more. Agent and alkaline neutralizer,
At the same time, it has been found that the method can be simply and quickly processed by the reaction and mixing method.

That is, a method has been found in which 2 mols or more of a reducing agent and 2 mols or more of an alkaline neutralizing agent are simultaneously added to and mixed with 1 mol of bromine remaining therein to the reaction mixture after completion of the reaction. Was. This method is hereinafter referred to as “processing method”
.

The reducing agent used in this treatment method is a reducing agent used in a usual reduction reaction, and specifically, sodium hydrogen sulfite, sodium dithionite, sodium sulfite, oxalic acid, hydrogen sulfide , Sodium nitrite, potassium nitrite, hydroxylamine sulfate,
Examples include tin, stannous oxide, and hydrazine. Of these, sodium bisulfite, sodium dithionite, sodium sulfite, oxalic acid, and sodium nitrite are 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 neutralizing agent 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. Also,
These alkaline neutralizing agents are used alone or in combination of two or more.

In the treatment method of the present invention, 2 mol or more, preferably 2 mol, per mol of residual bromine in the reaction mixture.
~ 30 mol, more preferably 2.2-15 mol, even more preferably 2.5-10 mol of reducing agent are added to the reaction mixture. When the amount of the reducing agent to be added is less than 2 mol, bromine remains in the mixture, and a low-purity brown-colored bromine compound is obtained, which is not preferable. Also,
2 moles or more based on 1 mole of residual bromine in the reaction mixture,
Preferably 2 to 50 mol, more preferably 2.2 to 30
Moles, more preferably 2.5 to 20 moles of an alkaline neutralizing agent are added to the reaction mixture. When the amount of the neutralizing agent to be added is less than 2 mol, hydrogen bromide remains in the aqueous solution, and this strong acid aqueous solution cannot be discarded as it is. In addition, some hydrogen bromide remains in the mixture, which easily corrodes metals. Furthermore, this hydrogen bromide has a strong irritating odor, which is not preferable in a working environment.

The reducing agent and the alkaline neutralizing agent are as follows:
The bromine compound and the bromine-containing reaction mixture are simultaneously added. Such a reducing agent and a neutralizing agent may be added separately or in advance, but it is preferable to add them separately since there is no possibility that the reducing agent may cause a side reaction due to alkali. Here, simultaneous addition does not strictly mean that both are added at the same time exactly, but at least 10 minutes, preferably 5 minutes after one agent is added and this agent is added. Means that the other agent ends the addition. As the addition method, a method in which a reducing agent is added and a neutralizing agent is immediately added immediately thereafter is preferably adopted.

In the treatment method, the reaction mixture to which the reducing agent and the alkaline neutralizing agent are added is mixed so that the reducing and neutralizing reactions proceed smoothly. As a method of mixing, various mixers can be used. For example, a method of stirring by rotating a stirring blade (one in which the center axis of the tank and the stirring axis coincide, one in which the stirring axis is inclined,
In-line mixers such as a stirrer using a stirring shaft on the side wall of the tank, a method of stirring by shaking the tank, a method of circulating the liquid in the tank by a pump, and a static mixer are used. In particular, a stirring tank is preferably used.

The weight ratio of the reaction mixture to the aqueous phase at the time of performing the reduction and neutralization reactions is 20:80 to 80:
20 is preferable, 30:70 to 70:30 is more preferable, and 40:60 to 60:40 is particularly preferable. Within this range, the reduction and neutralization reactions proceed efficiently, and bromine is removed in a short time. Therefore, when performing reduction and neutralization reactions,
It is preferable to add water or a solvent to the reaction mixture so as to fall within the above range.

The time required for the reduction and neutralization of bromine in the reaction mixture is preferably 2 minutes or more, more preferably 2 to 90 minutes, still more preferably 5 to 60 minutes, and more preferably 10 to 45 minutes.
Minutes are particularly preferred. Thus, in the present invention, the number of times of washing with water is only one step after the completion of the reduction and neutralization reactions. Therefore, in the reduction and neutralization reactions, the number of process operations is reduced, and thus the process control is facilitated.

The desired bromine compound is recovered from the reaction mixture treated by the above-mentioned method by a method known per se, for example, precipitation with a poor solvent. Separation and recovery of the target bromine compound from the reaction mixture obtained by the above-mentioned bromination reaction can also be carried out by performing a reduction treatment using a static mixer and then a neutralization treatment, as described below. it can.

That is, this method is a method of reducing and treating bromine by mixing a reaction mixture containing a target bromine compound and residual bromine with an aqueous solution containing a reducing agent, wherein the solution containing the bromine compound and bromine is treated. And the aqueous solution containing the reducing agent are introduced into a static mixer having 4 to 20 elements so that the flow rate of the mixed solution becomes 5 cm / sec or more, and the residence time in the static mixer is reduced. 3
This is a method for treating a reaction mixture in which mixing is performed within 00 seconds, and then the mixed solution derived from the static mixer is charged into a stirring tank having a capacity of 20 times or more the capacity of the static mixer, and then neutralized.

As the reducing agent used in this treatment method, those exemplified above are used, and the amount of the reducing agent is preferably 2 mol or more per mol of the residual bromine, and is preferably 2 to 100 mol.
Mole is more preferable, and 2 to 50 mole is still more preferable.
2-20 moles are particularly preferred. If the amount is less than 2 mol, the reduction reaction becomes insufficient and bromine tends to remain.

In the reduction reaction for bromine, the reaction mixture and an aqueous solution containing a reducing agent must be efficiently mixed. Therefore, when a normal stirring device is used, the stirring efficiency is not sufficient, and it is necessary to repeat the reaction several times in order to complete the reduction reaction. Therefore, by using a static mixer as a mixer, mixing can be performed efficiently, and bromine can be processed in a short time with a simple device.

As a condition for using a static mixer, the degree of substantial mixing can be determined by the number of elements in the tube, and the mixing is usually performed by dividing the number of elements as a power of two. It is considered that the mixing efficiency may be affected by factors such as the flow rate of the liquid component into the pipe, the viscosity, the Reynolds number, and the like, but the flow rate is particularly important. In this treatment method, the mixed solution of the reaction mixture and the aqueous solution containing the reducing agent is introduced into the static mixer such that the flow rate at the inlet of the static mixer is 5 cm / sec or more, preferably 10 cm / sec or more. I do. Flow velocity is 5
If it is lower than cm / sec, the mixing efficiency becomes insufficient and the reduction reaction is not sufficiently performed. In addition, when the flow rate is 500
Even if the mixture is introduced into the static mixer at more than cm / sec, the mixing efficiency is not substantially different, and no further flow rate is required.
Here, as for the flow rate, the addition rate of the reaction mixture introduced into the static mixer is A (mL / sec), the addition rate of the aqueous solution containing the reducing agent is B (mL / sec), and the sectional area of the static mixer is When C (cm ² ), (A + B)
/ C (cm / sec).

The method for introducing the reaction mixture or the aqueous solution containing the reducing agent into the static mixer is not particularly limited, and may be introduced using a dropping funnel. It is also preferable to supply a constant volume by a pump within a fixed time.

The number of elements of the static mixer is in the range of 4 to 20, and if the number of elements is 3 or less, mixing is not sufficient, the purity of the obtained bromine compound is low, and the mixing efficiency is 21 or more. No number of elements is required.

The residence time of the mixed solution of the reaction mixture introduced into the static mixer and the aqueous solution containing the reducing agent in the static mixer is within 300 seconds, and the residence time is within 0.1 second.
001 to 300 seconds are preferred, 0.005 to 180 seconds are more preferred, 0.01 to 120 seconds are still more preferred,
0.05 to 60 seconds is more preferable, and 0.1 to 10 seconds is particularly preferable. If the residence time is too long, liquid separation between the organic solvent phase and the aqueous phase becomes difficult, which is not preferable. Here, the residence time is defined as A (mL / sec), the addition rate of the reaction mixture introduced into the static mixer, and B (mL / sec), the addition rate of the aqueous solution containing the reducing agent. When the product is X (cm ³ ), X / (A + B)
(Seconds).

In the treatment method, the reaction mixture and the aqueous solution containing the reducing agent mixed in the static mixer are further derived from the static mixer, and the mixed solution is used in an amount of 20 times or more the capacity of the static mixer. Pour into a stirred tank with capacity.

At this time, a part of the reduction reaction proceeds by mixing the reaction mixture and an aqueous solution containing a reducing agent in a static mixer.
In order to release the heat of reaction in the static mixer, it is necessary to introduce such a mixed solution into another stirring tank. Here, the stirring tank may be any as long as it continuously holds the solution mixed in the static mixer in a state of a mixed solution, and the stirring method is not limited, for example, rotating a stirring blade. Agitation method (one that matches the center axis of the tank with the stirring axis, one that inclines the stirring axis,
For example, a method in which a stirring shaft is provided on the side wall of the tank, a method in which stirring is performed by swinging the tank, a method in which the liquid in the tank is circulated by a pump, and the like are used.

The capacity of the stirring tank is 20 times or more the capacity of the static mixer, and preferably has a capacity of 30 times or more. Further, the upper limit of the size of the stirring tank is not particularly limited, but the capacity of the static mixer is not limited to 20.
A stirring tank of less than 000 times is sufficient,
It is not economically preferable to use a stirring tank exceeding 000 times. The stirring tank having such a large capacity has a function of completing the reduction reaction by stirring and mixing, and also has a function of radiating reaction heat generated when reacting in the static mixer in the stirring tank. In addition, a pipe was installed from the stirring tank to the inlet of the static mixer,
The solution in the stirring tank may be re-introduced into the static mixer.

The stirring time of the solution in the stirring tank is preferably 2 minutes or more, more preferably 2 to 90 minutes, still more preferably 3 to 60 minutes, and particularly preferably 5 to 45 minutes. The reduction reaction is completed by stirring and mixing for such a period of time.

After the completion of the reduction reaction, bromine turns into hydrogen bromide, most of which is dissolved in an aqueous solution containing a reducing agent, and becomes acidic water having a relatively low pH. In such a state, the target bromine compound may be recovered, but since the reaction apparatus is usually made of metal, it often causes safety problems such as corrosion by acid and perforation. It is preferable to neutralize hydrogen chloride, and an alkaline neutralizer is preferably used.

Examples of the alkaline neutralizing agent include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates as described above. Specifically, 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 neutralizers are used alone or in combination of two or more.

In this case, the residual bromine 1 in the reaction mixture was
2 mol or more, preferably 2 to 100 mol, more preferably 2 to 50 mol, and still more preferably 2 mol,
２０20 moles of an alkaline neutralizing agent is mixed with the solution after the completion of the reduction reaction. At this time, the pH of the solution is preferably 7.5 or more, and more preferably 8 or more. If the amount of the neutralizing agent to be added is less than 2 mol, hydrogen bromide remains in the aqueous solution, and this strong acid aqueous solution cannot be discarded as it is. Also, hydrogen bromide partially remains in the bromine compound, and this corrodes the metal. Further, this bromine compound has a strong pungent odor and is not preferable in a working environment.

The time required for the neutralization reaction is preferably 2 minutes or more, more preferably 2 to 90 minutes, further preferably 5 to 60 minutes, and particularly preferably 10 to 45 minutes. The bromine compound obtained by the method of the present invention is recovered by an appropriate method well known to those skilled in the art, for example, precipitation with a poor solvent.

Thus, according to the method of the present invention, the following general formula (2) wherein the unsaturated group of the unsaturated compound is saturated by a bromine atom by the bromination reaction of the unsaturated compound represented by the general formula (1) ) Is obtained as a highly pure bromine compound. During ^{R 3 -O-Ar 1 -Y-} Ar 2 -O-R 4 (2) ( wherein, Ar ^1, Ar ² and Y are the same meaning defined in the general formula (1) .R ³ and R ⁴ means a group in which the unsaturated group in R ¹ and R ² in the general formula (1) is saturated with a bromine atom.

The bromine compound obtained by the present invention has a purity of 80% by weight or more, preferably 85% by weight or more, and particularly preferably 90% by weight or more. Such a high-purity bromine compound is extremely excellent as a flame retardant for a thermoplastic resin.

The bromine compound obtained by the method of the present invention not only has excellent purity, but also has excellent quality in that, when used as a flame retardant, the content of impurities having a bad effect is small.

That is, in the obtained bromine compound, the following general formula (4) (In the formula, Ar ¹ , Ar ² and Y have the same meanings as defined in the general formula (1). 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, and (p +
q) represents 1 or more, preferably an integer of 2 to 10, s and t each represent an integer of 0 to 5, and (s + t) represents 1
Above, preferably an integer of 1 to 5 is shown. )) Is contained in a small amount.

In the bromine compound of the present invention, the content of the hydroxybromine compound represented by the above formula (4) is 0.02 relative to 1 mol of the bromine compound represented by the above formula (1).
Mol or less, preferably from 0.0001 to 0.02 mol, more preferably from 0.0001 to 0.015 mol, more preferably from 0.001 to 0.015 mol.
0001-0.01 mol is more preferred. If the content of the compound represented by the formula (4) exceeds 0.02 mol with respect to 1 mol of the bromine compound represented by the formula (1), the thermal stability of the bromine compound of the present invention is undesirably reduced. .

The compound represented by the formula (4) reacts the above-mentioned unsaturated bond compound with bromine to synthesize a bromine compound represented by the formula (1).
The intermediate formed by the reaction of bromine with water present in a reaction solution consisting essentially of bromine or a bromine solution and an alcohol compound is a by-product formed by reacting with the unsaturated bond compound.

In particular, when the bromination reaction in the method of the present invention is carried out by adding an alcohol represented by the above general formula (3), the obtained bromine compound is not only high in purity but also thermally stable. It has a small proportion of an alkoxybromine compound represented by the following general formula (5) which does not adversely affect the properties.

[0112] (In the formula, Ar ¹ , Ar ² and Y have the same meanings as defined in the general formula (1). R ⁶ and R ⁷ are the same or different and represent a hydrocarbon group having 2 to 11 carbon atoms.)
p, q, s and t have the same meanings as defined in the general formula (4). R ⁸ and R ⁹ each have 1 carbon atom
And represents 6 to 6 aliphatic groups. )

As described above, in the compound represented by the formula (5), the intermediate formed by the reaction between the alcohol represented by the formula (3) and bromine reacts with the aliphatic unsaturated group of the unsaturated compound. By-products
This by-product does not adversely affect the thermal stability of the bromine compound. The content of the alkoxy bromine compound represented by the formula (5) is preferably 0.01 to 0.2 mol, and preferably 0.01 to 0.1 mol, per 1 mol of the bromine compound represented by the formula (1).
5 mol is more preferable, 0.01 to 0.1 mol is further preferable, and 0.01 to 0.05 mol is particularly preferable. When the content of the alkoxybromine compound represented by the formula (5) is
When the amount is not more than 0.2 mol relative to 1 mol of the bromine compound represented by the formula (1), the flame retardancy of a resin composition containing the bromine compound as a flame retardant is not adversely affected, which is preferable.

[0114]

The present invention will be described below in detail with reference to examples. In the examples, the compound having an aliphatic unsaturated bond represented by the general formula (1) may be abbreviated as “raw material”. Further, the measurement of the purity, the bromine content, and the specific gravity were performed according to the following methods. (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 are measured by high performance liquid chromatography (Shimadzu Corporation 280 by SCL-6B)
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, 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 bromine content The sample was heated with fuming nitric acid in a closed vessel to decompose it, and the generated hydrobromic acid was quantified by titration with silver nitrate (Carius method). analyzed.

(3) Specific gravity The specific gravity was measured at 20 ° C. using a glass specific gravity bottle.

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

(5) 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 at the bottom was 0.1 μm).
In a hot air circulation dryer at 70 ° C.
After heating for an hour, the petri dish was taken out and cooled to room temperature. When the solid sample in the Petri dish slides, lift the other side while the Petri dish is in contact with the horizontal surface on one side, and tilt it. (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 °,
The sample has insufficient thermal stability, which means that a blocking phenomenon is likely to occur.

In the following Examples and Comparative Examples, the raw material N
o. (1) to (6) mean the following compounds, respectively. Raw material No. Compound name No. (1); 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane No. (2); 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane No. (3); bis {(3,5-dibromo-4-allyloxy) phenyl} methane No. (4); bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane No. (5); (3,3 ', 5,5'-tetrabromo-4,4'-diallyloxy) biphenyl No. (6); bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone No. (7); bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone

Example 1 In a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,2-bis {(3,5-
Dibromo-4-allyloxy) phenyl @ propane 13
5 g (0.216 mol) and 230 g of methylene chloride dehydrated with synthetic zeolite were added and dissolved (the specific gravity of this solution was 1.47, and the concentration calculated therefrom was 0.8).
7 mol / L). The solution is stirred and 39-4
While refluxing methylene chloride at a temperature of 1 ° C, bromine 7
2.7 g (0.455 mol) was added dropwise from the dropping funnel in 8 minutes (the rate of addition of bromine was 4.4 per mol of the starting material).
mmol / sec). After completion of the dropwise addition, the reaction solution is heated to 39 to 41 ° C.
The mixture was continuously stirred for 30 minutes while refluxing methylene chloride at the temperature described above to complete 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 methylene chloride was separated from the methylene chloride layer.
%, And 500 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to collect a massive solid. This massive solid is crushed in a mortar,
After drying under reduced pressure at 5 mmHg for 19 hours, 198.5 g of a product was obtained (yield 97.2%).

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that no allyl group absorption was observed. From the above analysis results, the product is
It was confirmed that the substance was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.8% and a melting point of 1
At 10 ° C., the bromine content was 67.5% (theoretical 67.8%).

Example 2 In a 1 L glass reaction vessel used in Example 1, 2,2
-Bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane 140.8 g (0.216 mo
l) and methylene chloride 16 dehydrated with synthetic zeolite
A mixed solvent of 3 g and 70 g of 1,4-dioxane was added and dissolved (specific gravity of the solution was 1.35). This solution was stirred, and 79.5 g of bromine (0.497 m
ol) was dropped from the dropping funnel in 9 minutes (the rate of addition of bromine was 1.09 mmol / sec with respect to 1 mol of the raw material). After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes while refluxing the mixed solvent to terminate the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain 203.3 g of a white solid product (yield 96.8%). The product obtained in the same manner as in Example 1 ¹ H-
As a result of analysis using NMR and FT-IR, the product was found to be 2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. confirmed. This bromine compound has a purity of 9
The bromine content was 6.5% (theoretical 65.8%).

Example 3 In Example 2, 2,2-bis {(3,5-dibromo-
Using bis (3,5-dibromo-4-allyloxy) phenyl} methane (128.7 g, 0.216 mol) instead of 4-isobutenyloxy) phenyl {propane (specific gravity of solution: 1.34), bromine Bromination was carried out in the same manner as in Example 2 except that 79.5 g was dropped in 8.3 minutes instead of 9 minutes, to obtain 191.4 g of the product (yield 96.7%). .

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, the product was identified as bis {3,5-dibromo-4- (2,3-dibromo-
(Propyloxy) phenyl @ methane was confirmed. The bromine compound had a purity of 96.7% and a bromine content of 69.5% (theoretical value: 69.8%).

Example 4 In Example 1, 2,2-bis {(3,5-dibromo-
134.8 g (0.216 mol) of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane instead of 135 g of 4-allyloxy) phenyl {propane
Was used (bromination was carried out in the same manner as in Example 1 except that the specific gravity of the solution was 1.47) to obtain 197.6 g of a product (yield 96.9%).

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, the product was identified as bis {3,5-dibromo-4- (2,3-dibromo-
2-methylpropyloxy) phenyl @ methane was confirmed. This bromine compound has a purity of 96.8%,
The bromine content was 67.7% (theoretical 67.8%).

Example 5 In Example 1, 2,2-bis {(3,5-dibromo-
Instead of 135 g of (4-allyloxy) phenyl} propane, 125.7 g of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl (0.216 mol
Bromination was carried out in the same manner as in Example 1 except that 1) was used (specific gravity of the solution was 1.47) to obtain 186.6 g of a product (yield: 95.8%).

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, the product was identified as {3,3 ′, 5,5′-tetrabromo-4,4′-
(2,3-Dibromo-propyloxy)} biphenyl was confirmed. The compound has a purity of 95.7%,
The bromine content was 70.8% (theoretical 70.9%).

Example 6 In Example 1, 230 g of methylene chloride was replaced with 86 g (specific gravity of the solution was 1.42), and 72.7 g of bromine was 75 g.
(0.469 mol), followed by bromination in the same manner as in Example 1 to obtain 199.5 g of the product (yield 97.7%). The product obtained in the same manner as in Example 1 ¹ H-
As a result of analysis using NMR and FT-IR, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.7%.

Example 7 In Example 1, 2,2-bis {(3,5-dibromo-
135 g of 4-allyloxy) phenyl @ propane in 26
Instead of 8 g (0.430 mol), methylene chloride 23
The bromination was carried out in the same manner as in Example 1 except that 0 g was replaced with 493 g (specific gravity of the solution was 1.42) and 72.7 g of bromine was replaced with 80 g (0.500 mol).
2.8 g were obtained (96.9% yield).

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.8%.

Example 8 In Example 1, 2,2-bis {(3,5-dibromo-
135 g of 4-allyloxy) phenyl @ propane in 16
Instead of 2 g (0.260 mol), methylene chloride 23
Bromination was carried out in the same manner as in Example 1 except that 0 g was replaced by 234 g (specific gravity of the solution was 1.47), and 72.7 g of bromine was replaced by 95 g (0.594 mol).
4.7 g were obtained (95.8% yield).

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, it was confirmed that the product was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound had a purity of 96.6%.

Example 9 In Example 1, 2,2-bis {(3,5-dibromo-
4-isobutenyloxy) phenyl @ propane 140.
Instead of 8 g, 148 g of bis {3,5-dibromo-4-isobutenyloxy) phenyl} sulfone (0.22
0 mol) and using 230 g of methylene chloride as 121 g
Instead of (specific gravity of the solution 1.41), 72.7 g of bromine was added to 7
Example 1 except that 2.0 g (0.451 mol) was used instead.
Bromination was carried out in the same manner as described above to obtain 206.9 g of a product (yield: 94.8%).

The product obtained in the same manner as in Example 1 was treated with ¹ H-
As a result of analysis using NMR and FT-IR, the product was identified as bis {3,5-dibromo-4- (2,3-dibromo-
2-methylpropyloxy) sulfone was confirmed. The compound had a purity of 95.3% and a bromine content of 64.1% (theoretical 64.4%).

Comparative Example 1 In Example 1, bromine was dropped over 120 minutes.
Except for performing a bromination reaction without refluxing methylene chloride at a reaction temperature of 20 ° C. while cooling (per mole of raw material,
The rate of bromine addition was 0.29 mmol / sec).
As a result, the yield of the obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was 96.5%. Its purity was as low as 89.7%.

Comparative Example 2 The procedure of Example 1 was repeated, except that the bromination was carried out by dropping bromine over 120 minutes (the rate of addition of bromine was 0.29 mmol / sec per mole of raw material). Was performed in the same manner as described above. At this time, the solution temperature at the start of the dropping of bromine is 2
Although the temperature was 0 ° C., as the bromine was added dropwise, the solution temperature gradually increased due to the heat of reaction, and at the end of the addition, the solution temperature reached 3 ° C.
The temperature reached 7 ° C. The reaction vessel was not cooled and methylene chloride did not reflux. The resulting 2,2-bis3,
The purity of 5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was as low as 63.0%.

The results of Examples 1 to 9 and Comparative Example 1 are shown in Tables 1 and 2. Here, the solvents (A) and (B) have the following composition. (A) methylene chloride (B) methylene chloride / 1,4-dioxane = 70/30
(Weight ratio) The addition rate is the rate of addition of bromine to 1 mol of the raw material.

[0141]

[Table 1]

[0142]

[Table 2]

Example 10 In a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,2-bis {(3,5-
Dibromo-4-allyloxy) phenyl @ propane 13
5 g (0.216 mol) and 230 g of methylene chloride dehydrated with a synthetic zeolite were added and dissolved. In this solution, 0.36 g of methanol (0.0113 g) was added.
mol) (the number of hydroxyl groups is 2.6 per 100 aliphatically unsaturated groups). The water content in this solution was 200 ppm (the number of water molecules was 0.9 per 100 aliphatic unsaturated groups).
4). Next, this solution was cooled to about 2 ° C., and 72.7 g (0.455 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 complete 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 produced hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and 90% of methylene chloride was separated from the methylene chloride layer.
The reaction product was precipitated by adding 500 mL of methanol thereto, and the precipitate was filtered to obtain a massive solid. This massive solid is crushed in a mortar,
It was dried under reduced pressure at 5 mmHg for 3 hours to obtain 198.5 g of a product (yield: 97.0%).

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that 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-
It was confirmed to be dibromopropyloxy) phenyl @ propane. This bromine compound has a purity of 95.1%, and impurities derived from water are contained in 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane per mole. 0.004 mol, and the impurity derived from methanol was 0.015 mol. Also,
The inclination angle of the bromine compound was 44 °.

Example 11 In Example 10, 0.36 g of ethanol (0.00783 mol, aliphatic unsaturated group 10) was used instead of methanol.
The same method as in Example 10 was carried out, except that the number of hydroxyl groups per 0 (1.8) was used, and 2,2-bis @ 3,5
-Dibromo-4- (2,3-dibromopropyloxy)
Phenyl｝ propane was obtained. This bromine compound has a purity of 9
5.3%, 2,2-bis {3,5-dibromo-4- (2,3
Impurities derived from water were 0.004 mol, and impurities derived from ethanol were 0.013 mol, per 1 mol of -dibromopropyloxy) phenyl @ propane.

Example 12 In Example 10, 2.33 g (0.0388 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 9.0) of i-propanol was used in place of methanol, and the initial temperature of the reaction solution was changed. Was carried out in the same manner as in Example 10 except that the temperature was changed to 25 ° C. At the end of the bromine addition, the temperature of the reaction solution is 3
6 ° 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 an impurity 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 i-propanol was 0.037 mol.

Example 13 In Example 12, n-propanol was used instead of n-propanol.
Except that 1.13 g of butanol (0.015 mol, 3.5 hydroxyl groups per 100 aliphatic unsaturated groups) was used.
By a method similar to that in Example 12, 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was mainly obtained. This bromine compound has a purity of 94.9% and 2,2-bis {3,5-dibromo-4-.
With respect to 1 mol of (2,3-dibromopropyloxy) phenyl @ propane, 0.003 mol of impurities derived from water and 0.021 mol of impurities derived from n-butanol were used.

Example 14 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and 230 g of methylene chloride were placed in the glass reaction vessel used in Example 10. Dissolved. Further, 0.72 g (0.0157 mol) of ethanol was added to this solution (the number of hydroxyl groups per 100 aliphatic unsaturated groups: 3.6).
Ko). The water content in this solution was 500 ppm (2.4 water molecules per 100 aliphatic unsaturated groups). The solution is then cooled to about 2 ° C. and, with stirring, bromine 7
2.7 g (0.455 mol) was added dropwise from the dropping funnel over 60 minutes. At the end of dropping, the temperature of the reaction solution is 16 ° C.
Met. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 10 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
For 1 mol of -bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane, 0.005 mol of impurities derived from water and 0.016 mol of impurities derived from ethanol. Met. The inclination angle of the bromine compound was 45 °.

Example 15 The procedure of Example 10 was repeated, except that the bromine was dropped for 120 minutes.
After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes, and the same method as in Example 10 was carried out except that the reaction solution was cooled so as to keep the temperature of the reaction solution at 20 ° C during the bromination reaction. -Bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 95.2%, and the impurity derived from water is 0.1 mol per mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. 003 mol, impurities derived from methanol are 0.01
It was 5 moles.

Example 16 In Example 10, 0.72 g (0.016 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 3.6) of methylene chloride was used instead of methanol, instead of methanol.
g to 615 g (water content in this solution is 200 pp
m, number of water molecules per 100 aliphatic unsaturated groups: 1.9
E), the reaction temperature was set at 39 to 41 ° C., and 80.0 g (0.501 mol) of bromine was added dropwise over about 5 minutes while refluxing the solvent. After completion of the bromine addition, 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 10, and was mainly treated with 2,2-
Bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 96.1% and 2,2-bis {3,5-dibromo-4.
The impurity derived from water is 0.003 per 1 mol of-(2,3-dibromopropyloxy) phenyl} propane.
The impurity derived from mol and methanol was 0.016 mol. The inclination angle of the bromine compound was 41 °.

Example 17 Into the glass reaction vessel used in Example 10, 135 g (0.207 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane and synthetic zeolite were added. 230 g of methylene chloride dehydrated in the above was added and dissolved. Also, in this solution, methanol was added.
36 g (0.0113 mol) were added (the number of hydroxyl groups per 100 aliphatic unsaturated groups: 2.7). The water content in this solution was 200 ppm (0.98 water molecules per 100 aliphatic unsaturated groups). Next, this solution is heated to about 2 ° C.
72.0 g of bromine (0.419 m
ol) 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 complete the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 10 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- (2,3
-Dibromo-2-methylpropyloxy) phenyl @ propane / mol of water contained impurities of 0.00
The impurity derived from 3 moles and methanol was 0.019 moles.

Example 18 135 g (0.209 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone and 230 g of methylene chloride were placed in the glass reaction vessel used in Example 10. Dissolved. Further, 1.54 g (0.0335 mol) of ethanol was added to this solution (the number of hydroxyl groups per 100 aliphatic unsaturated groups: 8.0).
Ko). The water content in this solution was 500 ppm (2.4 water molecules per 100 aliphatic unsaturated groups). The solution is then cooled to about 2 ° C. and, with stirring, bromine 8
0.0 g (0.501 mol) was added dropwise from the dropping funnel over 60 minutes. At the end of dropping, the temperature of the reaction solution is 16 ° C.
Met. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 10 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%, 2,
2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone per mole,
The impurity derived from water was 0.005 mol, and the impurity derived from ethanol was 0.040 mol.

Example 19 Bis {(3,5-dibromo-4-allyloxy) phenyl} was added to the glass reaction vessel used in Example 10.
135 g (0.227 mol) of methane and 230 g of chloroform dehydrated with synthetic zeolite were added and dissolved. In addition, n-propanol 2.33 was added to this solution.
g (0.0388 mol) (aliphatic unsaturated group 1)
The number of hydroxyl groups per 00 is 8.5). The water content in this solution was 200 ppm (the number of water molecules was 0.90 per 100 aliphatic unsaturated groups). Next, the solution was set at 25 ° C., and while stirring, 80.0 g of bromine (0.501 mol) was added.
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 complete the bromine addition reaction.

Next, the reaction solution was treated in the same manner as in Example 10 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%, 2,2-
With respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane, 0.003 mol of impurities derived from water and 0.003 mol of impurities derived from n-propyl alcohol are used. 036 mol.

Example 20 The glass reaction vessel used in Example 10 was charged with (3,3 ′,
135 g (0.232 mol) of 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl and 615 g of 1,4-dioxane dehydrated with a synthetic zeolite were added and dissolved. In this solution, ethanol 1.5 was added.
4 g (0.0335 mol) were added (7.2 hydroxyl groups per 100 aliphatic unsaturated groups). The water content in this solution was 400 ppm (3.6 water molecules per 100 aliphatic unsaturated groups). Next, the solution was set at 25 ° C., and while stirring, 80.0 g of bromine (0.501 mol) was added.
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 complete the bromine addition reaction.

Next, this reaction solution was treated in the same manner as in Example 10 to obtain {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3-dibromopropyloxy)} biphenyl. I got This bromine compound has a purity of 94.0%,
｛3,3 ', 5,5'-tetrabromo-4,4'-(2,3
The amount of impurities derived from water and the amount of impurities derived from ethanol were 0.005 mol and 0.032 mol, respectively, per 1 mol of -dibromopropyloxy) biphenyl.

The results of Examples 10 to 20 are shown in Tables 3 and 4. In Tables 3 and 4, the concentration of the compound having a hydroxyl group indicates the number of hydroxyl groups (100) per 100 unsaturated groups of the compound having an aliphatic unsaturated bond. The unsaturated group 100 of the compound having
The number of water molecules per unit (co) 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.

[0162]

[Table 3]

[0163]

[Table 4]

Example 21 72.6 g (0.45) of bromine was placed in a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
4 mol). Also, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane 135
g (0.216 mol) was dissolved in 230 g of methylene chloride (water content in this solution was 200 pp).
m and a water molecule of 0.94 per 100 aliphatic unsaturated groups.
Is). Next, while stirring the inside of the reaction vessel, 15-
At a temperature of 20 ° C., 365 g of a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped into bromine from a dropping funnel in 60 minutes. After the completion of the dropwise addition, the reaction solution was heated at a temperature of
Stirring was continued for another minute to complete the bromine addition reaction.

Next, excess bromine in the reaction solution was reduced with 100 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, the methylene chloride layer was separated from this solution, and 90 ml of methylene chloride was separated from the methylene chloride layer.
%, And the reaction product was precipitated by adding 500 mL of methanol, 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.

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that no allyl group absorption was observed. From the above analysis results, the product is
It was confirmed that the substance was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The bromine compound had a purity of 96.5% and a bromine content of 67.5% (theoretical value: 67.8%).

Example 22 72.6 g (0.45) of bromine was placed in a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
4 mol) and 58.1 g of methylene chloride. Next, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane at a temperature of 15 to 20 ° C. while stirring the inside of the reaction vessel.
g was dropped into the bromine solution from the dropping funnel in 60 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be 2,2-bis {3,5-
It was confirmed to be dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. The bromine compound had a purity of 96.3% and a bromine content of 67.5% (theoretical 67.8%).

Example 23 72.6 g (0.45) of bromine was placed in a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
4 mol) and 58.1 g of methylene chloride. Further, 140.8 g of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (0.216 g)
mol) was dissolved in 230 g of methylene chloride. Next, 15-20 ° C. while stirring the inside of the reaction vessel.
At the temperature of 2,2-bis {(3,5-dibromo-4)
370.8 g of a solution of -isobutenyloxy) phenyl @ propane in methylene chloride was added dropwise from the dropping funnel to the bromine solution in 120 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be 2,2-bis {3,5-
It was confirmed to be dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane. This bromine compound has a purity of 96.5% and a bromine content of 6%.
5.3% (theoretical 65.8%)

Example 24 In a 1 L glass reactor equipped with a stirrer, condenser, thermometer and dropping funnel, 72.6 g of bromine (0.45) were added.
4 mol) and 58.1 g of methylene chloride. A solution was prepared by dissolving 128.7 g (0.216 mol) of bis {(3,5-dibromo-4-allyloxy) phenyl} methane in a mixed solvent of 161 g of methylene chloride and 69 g of 1,4-dioxane. Next, the bis {(3,5-dibromo-4-allyloxy) phenyl} is stirred at a temperature of 15 to 20 ° C. while stirring the inside of the reaction vessel.
358.7 g of a methane solution was dropped into the bromine solution from the dropping funnel over 60 minutes. After completion of the dropwise addition, the reaction solution is heated to 15 to 20 ° C.
The stirring was continued for 30 minutes at this temperature to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, it was found that the product was bis {3,5-dibromo-4- (2,3-dibromo-propyloxy). ) It was confirmed to be phenyl methane. The bromine compound had a purity of 96.0% and a bromine content of 69.5% (theoretical value: 6).
9.8%).

Example 25 To a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 7.26 g of bromine (0.04 g) was added.
5 mol) and 217.7 g of methylene chloride.
Further, 13.5 g of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane (0.0216 mol
A solution in which 1) was dissolved in 23 g of methylene chloride was prepared.
Next, a solution of the bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane in methylene chloride at a temperature of 15 to 20 ° C. while stirring the reaction vessel.
5 g was dropped into the bromine solution from the dropping funnel in 60 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be bis {3,5-dibromo-4- (2,3-dibromo-2- It was confirmed to be methylpropyloxy) phenyl @ methane. The bromine compound had a purity of 96.2% and a bromine content of 67.7% (theoretical value: 67.8%).

Example 26 In a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g (0.45) of bromine was added.
4 mol) and 300 g of methylene chloride. Further, 125.7 g of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl (0.216 mol
A solution of l) dissolved in 230 g of methylene chloride was prepared. Next, while stirring the inside of the reaction vessel, at a temperature of 15 to 20 ° C., (3,3 ′, 5,5′-tetrabromo-4,
A solution of 45.7-diallyloxy) biphenyl in methylene chloride (355.7 g) was added dropwise from the dropping funnel to the bromine solution in 60 minutes. After the completion of the dropwise addition, the reaction solution was heated at a temperature of
Stirring was continued for another minute to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was identified as {3,3 ′, 5,5′-
It was confirmed to be tetrabromo-4,4 '-(2,3-dibromo-propyloxy) オ キ シ biphenyl. This bromine compound has a purity of 95.7%, a bromine content of 70.7%.
(Theoretical 70.9%).

Example 27 In a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g (0.45) of bromine was added.
4 mol) and 14.5 g of methylene chloride. A solution prepared by dissolving 139.5 g (0.216 mol) of bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone in 230 g of methylene chloride was prepared. Next, a solution of the bis {3,5-dibromo-4-allyloxy) phenyl} sulfone in methylene chloride at 369.
5 g was dropped into the bromine solution from the dropping funnel in 60 minutes. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be bis {3,5-dibromo-4- (2,3-dibromopropyloxy). It was confirmed to be phenyl persulfone. This bromine compound had a purity of 95.4% and a bromine content of 66.0% (theoretical value: 6).
6.2%).

Example 28 72.6 g (0.45) of bromine was placed in a 1-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
4 mol) and 58.1 g of methylene chloride. Also, 145.6 g of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone (0.216 mo
l) is treated with 161 g of methylene chloride and 69 of 1,4-dioxane.
g and a solution dissolved in a mixed solvent with g. Next, 375.6 g of such a solution of bis {3,5-dibromo-4-isobutenyloxy) phenyl} sulfone was stirred at a temperature of 15 to 20 ° C. from the dropping funnel for 120 minutes while stirring the inside of the reaction vessel. It was added dropwise to the bromine solution. After completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 to 20 ° C. for 30 minutes to complete the bromine addition reaction.

The obtained reaction solution was subjected to the same operation as in Example 21 to obtain a white solid product. The product obtained in the same manner as in Example 21 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be bis {3,5-dibromo-4- (2,3-dibromo-2- Methylpropyloxy)｝ sulfone was confirmed. The bromine compound had a purity of 95.0% and a bromine content of 64.1% (theoretical 64.4%). Tables 5 and 6 show the results of Examples 21 to 28.

[0181]

[Table 5]

[0182]

[Table 6]

Example 29 72.7 g of bromine was placed in a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
(0.455 mol). Also, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl}
135 g (0.216 mol) of propane was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g of methanol (0.0113 mol, 2.6 hydroxyl groups per 100 aliphatic unsaturated groups) was added thereto. Prepared solution. Next, the bromine in the reaction vessel is cooled to 2 ° C.
With stirring, the methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped into bromine 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. The water content in this reaction solution is 200 ppm
(The number of water molecules per 100 aliphatically unsaturated groups is 1.
1).

Next, excess bromine in the reaction solution was reduced with 50 g of a 15% by weight aqueous sodium bisulfite solution, and the produced hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, 100 g of ion-exchanged water was added, and after stirring, a methylene chloride layer was separated from the solution. About 90% of the methylene chloride was evaporated and removed from the methylene chloride layer, and 500 mL of methanol was added thereto to precipitate a reaction product. Then, the precipitate was filtered to take out a massive solid.
This lump solid is crushed in a mortar, 80 ° C., 3 hours, 5 mm
The product was obtained by drying under reduced pressure with Hg.

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that 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-
It was confirmed to be dibromopropyloxy) phenyl @ propane. The bromine compound had a purity of 96.7% and was 2,2-bis {3,5-dibromo-4- (2,3-
The amount of impurities derived from water was 0.0023 mol, and the amount of impurities derived from methanol was 0.0155 mol, per 1 mol of dibromopropyloxy) phenyl @ propane.
The inclination angle of the bromine compound was 40 °.

Example 30 In Example 29, 0.36 g of ethanol (0.00783 mol, aliphatic unsaturated group 10) was used instead of methanol.
A bromine addition reaction was carried out in the same manner as in Example 29, except that the number of hydroxyl groups per 0 (1.8) was used. The water content in this reaction solution was 210 ppm (1.2 water molecules per 100 aliphatic unsaturated groups).

The reaction solution was treated in the same manner as in Example 29 to obtain mainly 2,2-bis {3,5-dibromo-4-
(2,3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 96.1%,
With respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane, 0.0025 mol of impurities derived from water and 0 mol of impurities derived from ethanol are present. Was 0.0124 mole. The inclination angle of the bromine compound was 41 °.

Example 31 In a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g (0.45) of bromine was added.
4 mol) and 230 g of methylene chloride. In addition, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane
Was dissolved in 230 g of methylene chloride, and 0.36 g (0.00783 mol of an aliphatic unsaturated group 10
A solution to which the number of hydroxyl groups (1.8 per 0) was added was prepared. Next, the bromine solution in the reaction vessel is cooled to 2 ° C., and while stirring, the 2,2-bis {(3,5-dibromo-4)
A methylene chloride solution of (allyloxy) phenyl @ propane was dropped into the bromine solution 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. The water content in this reaction solution is 420 ppm
(The number of water molecules per 100 aliphatically unsaturated groups is 3.
6).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly 2,2-bis {3,5-dibromo-4- (2,3 -Dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 95.9% and has an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0041 mol and impurities derived from ethanol were 0.0124 mol. The inclination angle of the bromine compound was 44 °.

Example 32 In a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g (0.45) of bromine was added.
4 mol) and 230 g of methylene chloride. In addition, 135 g (0.216 mol) of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane
Was dissolved in 230 g of methylene chloride, and 0.36 g (0.00783 mol of an aliphatic unsaturated group 10
A solution to which the number of hydroxyl groups (1.8 per 0) was added was prepared. Next, while stirring the inside of the reaction vessel and refluxing methylene chloride at a temperature of 39 to 41 ° C.,
A methylene chloride solution of bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped from the dropping funnel into the bromine solution over 10 minutes. After the addition is completed, the reaction solution is
Reflux the methylene chloride at a temperature of 9 to 41 ° C for 30 minutes.
Stirring was continued for another minute to complete the bromine addition reaction. The water content in this reaction solution was 420 ppm (the number of water molecules was 3.6 per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly 2,2-bis {3,5-dibromo-4- (2,3 -Dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.4% and has an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0023 mol, and impurities derived from ethanol were 0.0123 mol.

Example 33 In a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g of bromine was added.
(0.454 mol), 230 g of methylene chloride dehydrated with synthetic zeolite and 0.36 g of ethanol (0.35 mol).
00783 mol, the number of hydroxyl groups (1.8) per 100 unsaturated aliphatic groups) was added. Next, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (135 g, 0.216 mol) was refluxed at a temperature of 39 to 41 ° C. while stirring the inside of the reaction vessel.
l) was added to the bromine solution over 5 minutes. After completion of the addition, the reaction solution was continuously stirred at a temperature of 39 to 41 ° C. for 30 minutes while refluxing methylene chloride, thereby completing the bromine addition reaction. The water content in this reaction solution was 210 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.2).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly 2,2-bis {3,5-dibromo-4- (2,3 -Dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.5% and has an impurity derived from water based on 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0021 mol, and the impurity derived from ethanol was 0.0135 mol.

Example 34 A 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with 72.7 g (0.45) of bromine.
5 mol). Also, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane 135
g (0.216 mol) was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g (0.0060 mol of i-propanol, 1 part of aliphatic unsaturated group 1) was added thereto.
A solution was prepared by adding (number of hydroxyl groups: 1.4 / 00). Next, the bromine in the reaction vessel was cooled to about 2 ° C., and a solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was added from a dropping funnel over 60 minutes while stirring. It was added dropwise to bromine. At the end of the dropwise addition, the temperature of the reaction solution was 20 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction. The water content in this reaction solution was 200 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.1).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly 2,2-bis {3,5-dibromo-4- (2,3 -Dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.3% and has an impurity derived from water with respect to 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0019 mol, and the impurity derived from i-propanol was 0.0146 mol. The inclination angle of the bromine compound was 40 °.

Example 35 A 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with 72.7 g (0.45) of bromine.
5 mol). Also, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane 135
g (0.216 mol) was dissolved in 615 g of chloroform dehydrated with synthetic zeolite, and 0.54 g (0.0169 mol of methanol, 100
A solution was prepared by adding 3.9 hydroxyl groups / co).
Next, the bromine in the reaction vessel is cooled to 2 ° C., and while stirring, the chloroform solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is added to 6 mL of chloroform.
The bromine was added dropwise from the dropping funnel over 0 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. The water content in this reaction solution was 100 ppm (the number of water molecules per 100 aliphatic unsaturated groups: 1.1).

Next, the excess bromine in the reaction solution was
After reduction with 50 g of a 50% aqueous sodium bisulfite solution
Hydrogen bromide using 25 wt% sodium hydroxide aqueous solution
And neutralized. Thereafter, 200 g of ion-exchanged water was added and stirred.
After stirring, the chloroform layer was separated from this solution,
About 90% of chloroform is evaporated and removed from the chloroform layer
The reaction product was precipitated by adding 500 mL of methanol.
This precipitate was filtered, and a lump solid was taken out.
This lump solid is crushed in a mortar, 80 ° C., 3 hours, 5 mm
The product was obtained by drying under reduced pressure with Hg. As in Example 29,
The resulting product is ¹Using H-NMR and FT-IR
As a result of analysis, the product was mainly 2,2-bis @ 3,
5-dibromo-4- (2,3-dibromopropyloxy
C) It was confirmed to be phenyl @ propane. this
The bromine compound is 95.8% pure and 2,2-bis
{3,5-dibromo-4- (2,3-dibromopropylthio)
Xy) phenyl @ propane per mole, derived from water
Impurities were 0.0022 moles,
The pure product was 0.0155 mol.

Example 36 In a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 69.5 g of bromine were added.
(0.435 mol). Further, 135 g (0.207 mol) of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and methanol was added thereto. 36 g (0.0113 mol,
A solution was prepared by adding (the number of hydroxyl groups: 2.7) to 100 aliphatic unsaturated groups. Next, the bromine in the reaction vessel was reduced to about 2 ° C.
And a solution of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was dropped into the bromine 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. The water content in this reaction solution was 190 ppm (the number of water molecules per 100 aliphatic unsaturated groups: 1.1
Ko).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly 2,2-bis {3,5-dibromo-4- (2,3 -Dibromo-2-methylpropyloxy) phenyl} propane. This bromine compound has a purity of 95.8%,
2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane 1
The amount of impurities derived from water was 0.0021 mol, and the amount of impurities derived from methanol was 0.0212 mol, based on the mol.

Example 37 In a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 70.1 g of bromine was added.
(0.439 mol). Further, bis {3,5-dibromo-4-allyloxy) phenyl} sulfone 13
5 g (0.209 mol) was dissolved in 230 g of methylene chloride dehydrated with a synthetic zeolite, and 0.36 g (0.0113 mol, 100% of aliphatic unsaturated groups) of methanol was added thereto.
A solution was prepared by adding the number of hydroxyl groups per unit (2.7).
Next, the bromine in the reaction vessel was cooled to about 2 ° C., and a solution of bis {3,5-dibromo-4-allyloxy) phenyl} sulfone was dropped into the bromine from the dropping funnel over 60 minutes with stirring. At the end of dropping, the temperature of the reaction solution is 16
° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction. The water content in this reaction solution was 180 ppm (the number of water molecules was 1.0 per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 29 to obtain a white solid product. The product obtained in the same manner as in Example 29 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly bis@3.5
-Dibromo-4- (2,3-dibromopropyloxy)
It was confirmed to be phenyl persulfone. This bromine compound has a purity of 94.2%, and the impurity derived from water is 0.0020 with respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. Impurities derived from mol and methanol are 0.0
328 mol.

Example 38 76.2 g of bromine was placed in a 500-mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
(0.477 mol). In addition, 135 g of bis {3,5-dibromo-4-allyloxy) phenyl} methane
(0.227 mol) was dissolved in 615 g of chloroform dehydrated with synthetic zeolite, and 1.13 g (0.0157 mol of n-butanol, 100% of aliphatic unsaturated groups) were added to the solution.
A solution was prepared by adding 3.5 (number of hydroxyl groups per).
Next, the bromine in the reaction vessel was cooled to about 2 ° C., and a solution of bis {3,5-dibromo-4-allyloxy) phenyl} methane was dropped into the bromine from the dropping funnel over 60 minutes with stirring. At the end of the dropwise addition, the temperature of the reaction solution was 16 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes,
The bromine addition reaction was completed. The water content in the reaction solution was 100 ppm (the number of water molecules was 1.0 per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 35 to obtain a white solid product. The obtained product was analyzed by ¹ H-NMR and FT-IR in the same manner as in Example 29.
As a result of analysis using
It was confirmed to be 5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. This bromine compound has a purity of 94.9%, and the amount of impurities derived from water is 0.1 to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane.
0014 mol, impurities derived from n-butanol are 0.1%.
0353 mol.

Example 39 In a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 77.9 g of bromine (0.48) were added.
7mol) and 1,4 dehydrated with synthetic zeolite
-Dioxane 123g was charged. Also, (3,3 ', 5,
135 g (0.232 mol) of 5'-tetrabromo-4,4'-diallyloxy) biphenyl was dissolved in 615 g of 1,4-dioxane dehydrated with synthetic zeolite,
To this, 1.13 g of n-butanol (0.0157 mol,
A solution was prepared by adding 3.4 (number of hydroxyl groups) per 100 aliphatic unsaturated groups. Next, the bromine solution in the reaction vessel was set at about 22 ° C., and (3, 3 ′, 5, 5′-
A solution of tetrabromo-4,4'-diallyloxy) biphenyl was dropped into the bromine solution from the dropping funnel over 10 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 50 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction. The water content in this reaction solution was 12
It was 0 ppm (1.4 water molecules per 100 aliphatic unsaturated groups).

Next, excess bromine in the reaction solution was reduced with 50 g of a 15% by weight aqueous sodium bisulfite solution, and the produced hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, 100 g of ion-exchanged water was added, and after stirring, the 1,4-dioxane layer was separated from this solution.
The reaction product was precipitated by adding 500 mL of methanol thereto, and the precipitate was filtered to obtain a massive solid. This massive solid is crushed in a mortar,
The product was dried under reduced pressure at 5 mmHg for 3 hours to obtain a product. As in Example 29, the obtained product was analyzed by ¹ H-NMR and F
As a result of analysis using T-IR, the product was found to be mainly {3,3 ′, 5,5′-tetrabromo-4,4 ′-(2,3
-Dibromo-propyloxy)｝ biphenyl. This bromine compound has a purity of 94.6% and is {3,3 ′, 5,5′-tetrabromo-4,4′-
(2,3-dibromo-propyloxy) @biphenyl 1
The amount of impurities derived from water was 0.0018 mol, and the amount of impurities derived from n-butanol was 0.0254 mol, based on the mol.

Tables 7 and 8 show the results of Examples 29 to 39. In Tables 7 and 8, the concentration of the compound having a hydroxyl group indicates the number of hydroxyl groups (100) per 100 unsaturated groups of the compound having an aliphatic unsaturated bond. The unsaturated group 100 of the compound having
The number of water molecules per unit (co) 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.

[0207]

[Table 7]

[0208]

[Table 8]

Example 40 2,2-Bis {(3,5-dibromo-4-allyloxy)
Phenyl @ propane (raw material No. (1)) 1000g
(1.60 mol) in 1703 g (20.0 g) of methylene chloride.
mol). The specific gravity of this solution was 1.46, and the result of measurement by the Karl Fischer method was 160 ppm.
Water.

In a glass reactor equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 5.3 × 10 ⁻³ L / min. Was continuously added from the inlet 2 at a rate of 0.58 × 10 ⁻³ L / min (the molar ratio of bromine / compound (1) was 2.4).
5). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (1)
About 20 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 20.4 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution drawn out of the reaction vessel was
After reducing excess bromine with an aqueous sodium disulfite solution (about 15% by weight), the generated hydrogen bromide was neutralized with an aqueous sodium hydroxide solution. Then, 1000 g of ion-exchanged water was added to this solution.
, And the mixture is stirred. The methylene chloride layer is separated, and about 90% of methylene chloride is evaporated and removed from the methylene chloride layer.
Methanol was added to this to precipitate a reaction product, and this precipitate was filtered to take out a massive solid. This massive solid is crushed in a mortar, dried at 80 ° C. under reduced pressure for 10 hours,
Bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane was obtained. This bromine compound had a purity of 94.2% and a bromine content of 67.3% (theoretical value: 6).
7.8%).

Example 41 In Example 40, 1703 g of methylene chloride was added to 440 g of methylene chloride.
5g (51.8 mol) instead of (specific gravity of solution 1.42,
Example 40 except that the addition rate of the solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was adjusted to 10.5 × 10 ⁻³ L / min. The reaction was carried out in the same manner as described above. The resulting 2,2-
Bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.2%.

Example 42 In Example 40, a mixed solvent of 900 g (10.6 mol) of methylene chloride and 803 g (6.7 mol) of chloroform was used instead of 1703 g of methylene chloride (specific gravity of solution: 1.48, water-containing). The reaction was carried out in the same manner as in Example 40 except for the rate of 260 ppm). The obtained 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane has a purity of 94.0.
%Met.

Example 43 In Example 40, the rate of addition of the solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 135.2 × 10 ⁻³ L / min, and the addition of bromine was performed. Speed 1
The reaction was carried out in the same manner as in Example 40 except that 4.8 × 10 ⁻³ L / min was used. The resulting 2,2-bis {3,5-
Dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.1%.

Example 44 2,2-Bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (raw material No. (2)) 104
3 g (1.60 mol) was converted to 3400 g (4
0.0mol). The specific gravity of this solution was 1.46, and the result of measurement by the Karl Fischer method was 120 pp.
m of water.

In a glass reactor equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 10.5 × 10 ⁻³ L / min. Was continuously added at a rate of 0.59 × 10 ⁻³ L / min from the inlet 2 (the molar ratio of bromine / compound (2) was 2.0).
7). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (2)
About 11 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution drawn out from the reaction vessel is
Treated in the same manner as in Example 40, 2,2-bis @ 3,5
-Dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane was obtained. This bromine compound had a purity of 93.9%.

Example 45 Bis {(3,5-dibromo-4-allyloxy) phenyl} methane (raw material No. (3)) 476 g (0.8 mol)
l) was combined with 1700 g (20.0 mol) of methylene chloride and 1,
It was dissolved in a mixed solvent with 1700 g (19.3 mol) of 4-dioxane. This solution had a specific gravity of 1.22 and contained 320 ppm of water as measured by the Karl Fischer method.

In a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 10.6 × 10 ⁻³ L / min. Was continuously added from the inlet 2 at a rate of 0.43 × 10 ⁻³ L / min (the molar ratio of bromine / compound (3) was 3.1).
3). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (3)
About 11 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 10.9 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution drawn out of the reaction vessel was:
This was treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} methane. This bromine compound has a purity of 93.3.
%Met.

Example 46 Bis {(3,5-dibromo-4-isobutenyloxy)
500 g of phenyl methane (raw material No. (4))
8 mol) in 1700 g (20.0 mol) of methylene chloride.
l). The specific gravity of this solution was 1.41, and as a result of measurement by the Karl Fischer method, it contained 160 ppm of water.

In a glass reactor equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 10.5 × 10 ⁻³ L / min. Was continuously added from the inlet 2 at a rate of 0.62 × 10 ⁻³ L / min (the molar ratio of bromine / compound (4) was 2.2).
3). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (4)
About 11 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution drawn out from the reaction vessel was:
This was treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} methane. This bromine compound had a purity of 93.5%.

Example 47 Bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone (raw material No. (7)) (517 g, 0.8 g)
mol) in 1700 g (20.0 mol) of methylene chloride
Was dissolved. The specific gravity of this solution was 1.42, and as a result of measurement by the Karl Fischer method, it contained 180 ppm of water.

In a glass reaction vessel equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 10.5 × 10 ⁻³ L / min. Was continuously added from the inlet 2 at a rate of 0.59 × 10 ⁻³ L / min (the molar ratio of bromine / compound (7) was 2.1).
3). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (7)
About 11 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 10.8 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution derived from the reaction vessel was:
This was treated in the same manner as in Example 40 to obtain bis {3,5-dibromo-4- (2,3-dibromo-propyloxy) phenyl} sulfone. This bromine compound has a purity of 9
2.3%.

Example 48 466 g of (3,3 ′, 5,5′-tetrabromo-4,4′-diallyloxy) biphenyl (raw material No. (5))
(0.8 mol) in 1700 g (20.0 m) of methylene chloride
ol) and 1,700 g (19.3 mol) of 1,4-dioxane
l) and dissolved in a mixed solvent. The specific gravity of this solution is 1.2
0 and the result of measurement by the Karl Fischer method is 320
It contained ppm water.

In a glass reactor equipped with a stirring blade 3, a condenser 4 and a thermometer 5 shown in FIG. 2, the solution was introduced from the inlet 1 at a rate of 10.6 × 10 ⁻³ L / min. Was continuously added from the inlet 2 at a rate of 0.43 × 10 ⁻³ L / min (the molar ratio of bromine / compound (5) was 3.1).
6). The solution mixed in the reaction vessel generated heat due to the reaction heat of bromination, and the vaporized vapor was refluxed to the reaction vessel by the condenser 4 which was sufficiently cooled. Raw material No. (5)
About 11 minutes after starting the addition of the solution of
The reaction solution began to be drawn out from the outlet 8, and then continued to be drawn out continuously (residence time: 10.9 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution at a rate of 0.03 L /
Circulated into the reaction vessel at a rate of minutes.

The reaction solution derived from the reaction vessel was
Processed in the same manner as in Example 40, {3,3 ′, 5,5 ′
-Tetrabromo-4,4 '-(2,3-dibromo-propyloxy)} biphenyl was obtained. This bromine compound had a purity of 93.0%.

Example 49 In Example 40, the addition rate of a solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was set to 0.57 × 10 ⁻³ L / min, and bromine was added. The reaction was carried out in the same manner as in Example 1 except that the addition rate was 0.062 × 10 ⁻³ L / min. The resulting 2,2-bis3,
5-Dibromo-4- (2,3-dibromopropyloxy) phenyl} propane had a purity of 94.1%.

Comparative Example 3 2,2-bis {(3,5-dibromo-4-allyloxy)
The addition rate of the solution of phenyl-propane is 5.3 × 10 ^-3
Assuming a constant L / min, the bromine addition rate was 0.28 × 10 ⁻³ L / min (the bromine / compound (1) molar ratio was 1.18) for the first 10 minutes, and 0 for the next 10 minutes. .84 × 10 ^-3 L
/ Min (the molar ratio of bromine / compound (1) was 3.55), and the reaction was carried out for 40 minutes in the same manner as in Example 40, except that the addition was repeated. Raw material No.
About 20 minutes after the addition of the solution (1) and bromine was started, the reaction solution began to be drawn out from the outlet 8, and was continuously drawn out thereafter (residence time: 20.5 minutes). The reaction solution in the reaction vessel (120 ml) was pumped from a part of the reaction solution to 0.03 using the pump 6 from the time when the reaction solution began to be discharged.
Circulated into the reaction vessel at a rate of L / min.

The reaction solution derived from the reaction vessel was:
By treating in the same manner as in Example 40, 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was obtained. The bromine compound had a purity of 85.0%, and was a powder that easily adhered to each other and had poor storage stability.

Comparative Example 4 In Example 40, the addition rate of the solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was 5.3 × 10 ⁻³ L / min, and bromine was added. The addition rate is set to 0.4 × 10 ⁻³ L / min (bromine / raw material No. (1))
The reaction was carried out in the same manner as in Example 40 except for the molar ratio of 1.69), and the reaction was carried out in the same manner as in Example 40 to give 2,2-bis {3,5-dibromo-4- (2,3). (Dibromopropyloxy) phenyl} propane was obtained. The bromine compound had a purity of 71.0%, and was a powder that easily adhered to each other and had poor storage stability.

Comparative Example 5 2,2-bis {(3,5-dibromo-4-allyloxy)
1000 g (1.60 mol) of phenyl @ propane was dissolved in 1703 g (20.0 mol) of methylene chloride.
1694 g of this solution was placed in a 3000 ml glass container equipped with a stirring blade, a condenser, a thermometer and a dropping funnel, and 396 g of bromine was gradually dropped from the dropping funnel over 220 minutes with stirring. The solution temperature at the start of the dropping of bromine was 20 ° C., but as the bromine was dropped, the solution temperature gradually increased due to the heat of reaction, and reached 37 ° C. at the end of the dropping. During the addition of the bromine, the reaction vessel was not cooled, and the reflux of methylene chloride did not occur. After completion of the dropping of bromine, the reaction solution was treated in the same manner as in Example 40, and 2,2-bis @ 3,5-dibromo-4-.
(2,3-Dibromopropyloxy) phenyl} propane was obtained. The purity of the bromine compound was as low as 82.1%, the appearance was colored, and it was easy to adhere to each other and storage stability was poor.

Examples 40 to 49 and Comparative Examples 3 to
The results of No. 4 are shown in Tables 9 and 10. Table 9 and Table 1
0, the solvents (A) to (C) are: (A) methylene chloride (B) methylene chloride / chloroform = 53/47 (weight ratio) (C) methylene chloride / 1,4-dioxane = 50/50
(Weight ratio), and the concentration of water is mol% based on the number of moles of unsaturated groups in the raw material compound.

[0236]

[Table 9]

[0237]

[Table 10]

Example 50 A solution of 18.5 kg of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane in 50 kg of a methylene chloride solution was prepared in advance (specific gravity of the solution was 1.47, water content 150 ppm).

The adjusted methylene chloride solution was added to a static mixer (cross-sectional area: 0.5 cm ² ) having an internal volume of 20 cm ³ and consisting of 12 elements at an addition rate of 133.9 g / sec (91.1 mL / sec), and bromine was removed. The addition rate was 25.7 g / sec (8.3 mL / sec), that is, the flow rate of the mixed solution was 199.
cm / sec {(91.1 + 8.3) /0.5} continuously introduced into a static mixer and mixed [residence time in this static mixer is 0.5. 2
At 0 seconds {20 / (91.1 + 8.3)}], the mixed solution derived from the static mixer was charged into a 30 L stirring tank equipped with a condenser. In this stirring tank, the heat of reaction was released, and the vaporized vapor was refluxed to suppress the scattering of bromine. The mixed solution was continuously stirred in such a stirring tank, allowed to stay in the stirring tank for about 5 minutes, and then allowed to flow out of an overflow port of the stirring tank.

About 10 ml of the reaction solution flowing out of the overflow port was collected, and excess bromine was removed by 15% by weight.
25% by weight after reduction with 5 g of aqueous sodium bisulfite solution
And neutralized with an aqueous solution of caustic soda. After evaporating and removing most of the methylene chloride from the obtained methylene chloride layer,
The reaction product was precipitated by adding 50 mL of methanol, and the precipitate was filtered to remove a massive solid. This lump solid was pulverized in a mortar and dried under reduced pressure at 80 ° C. for 3 hours.
7 g were obtained.

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that no allyl group absorption was observed. From the above analysis results, the product is
It was confirmed that the substance was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 96.3% and a melting point of 1
At 14 ° C., the bromine content was 67.5% (theoretical 67.8%).

Example 51 Instead of the static mixer having an internal volume of 20 cm ³ and having 12 elements (cross-sectional area of 0.5 cm ² ), the static mixer having an internal volume of 10 cm ³ and having 6 elements (cross-sectional area) was used. The same reaction as in Example 1 was performed except that 0.5 cm ² ) was used (residence time in the static mixer was 0.10 seconds). This reaction product was prepared according to Example 1.
Analysis of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl}
It was confirmed to be propane. The bromine compound had a purity of 96.3%, a melting point of 114 ° C., and a bromine content of 67.6%.
5% (theoretical 67.8%).

Example 52 40 kg of a methylene chloride solution containing 14.8 kg of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was prepared in advance (the specific gravity of the solution was 1.4).
7, water content 150 ppm).

In a static mixer similar to that used in Example 50, the adjusted methylene chloride solution was added at a rate of 98.9 g / sec (67.3 mL / sec), and bromine was added at a rate of 22.4 g / sec ( 7.2 mL / sec), that is, continuously introduced into the static mixer so that the flow rate of the mixed solution was 149 cm / sec, and after mixing (residence time in this static mixer was 0.27 Seconds), the mixed solution derived from the static mixer was charged into a stirring tank having a capacity of 23 L equipped with a condenser. In this stirring tank,
The reaction heat was radiated, and the vaporized vapor was refluxed, whereby the scattering of bromine was suppressed. The mixed solution was continuously stirred in such a stirring tank, allowed to stay in the stirring tank for about 5 minutes, and then allowed to flow out of an overflow port of the stirring tank.

This reaction solution was treated in the same manner as in Example 50 to obtain 1.6 g of a reaction product. The product obtained in the same manner as in Example 50 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be 2,2-bis {3,5-dibromo-4- (2,3- Dibromo-2-methylpropyloxy) phenyl @ propane was confirmed.
This bromine compound has a purity of 94.0% and a bromine content of 65.3%.
% (Theoretical 65.8%).

Example 53 Bis {(3,5-dibromo-4-allyloxy)
Phenyl methane 14.8 kg methylene chloride solution 40
kg (the specific gravity of the solution was 1.47 and the water content was 200).
ppm).

In a static mixer similar to that used in Example 50, the adjusted methylene chloride solution was added at a rate of 79.8 g / sec (54.3 mL / sec), and bromine was added at a rate of 16.6 g / sec ( (5.4 mL / sec), that is, continuously introduced into the static mixer so that the flow rate of the mixed solution was 119 cm / sec, and after mixing (residence time in the static mixer was 0.34. Seconds), the mixed solution derived from the static mixer was charged into a 28-liter stirring tank equipped with a condenser. In this stirring tank,
The reaction heat was radiated, and the vaporized vapor was refluxed, whereby the scattering of bromine was suppressed. The mixed solution was continuously stirred in such a stirring tank, kept in the stirring tank for about 8 minutes, and then allowed to flow out of an overflow port of the stirring tank.

This reaction solution was treated in the same manner as in Example 50 to obtain 1.8 g of a reaction product. The product obtained in the same manner as in Example 50 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was identified as bis {3,5-dibromo-4- (2,3-dibromo-propyloxy ) It was confirmed to be phenyl methane. The bromine compound had a purity of 91.8% and a bromine content of 69.1% (theoretical value: 6).
9.8%).

Example 54 A mixed solvent solution of 14.8 kg of bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane in methylene chloride and 1,4-dioxane (methylene chloride / 1,
40 kg of 4-dioxane (70/30 weight ratio) was adjusted (the specific gravity of the solution was 1.35, and the water content was 250 ppm).

In a static mixer similar to that used in Example 50, the adjusted mixed solvent solution was added at a rate of 126.8 g / sec (93.9 mL / sec), and bromine was added at a rate of 28.8 g / sec ( 9.3 mL / sec), that is, continuously introduced into the static mixer such that the flow rate of the mixed solution was 206 cm / sec, and mixed (the residence time in the static mixer was 0.19. Seconds), the mixed solution derived from the static mixer was charged into a 30-L stirring tank equipped with a condenser. In this stirring tank, the reaction heat was radiated, and the vaporized vapor was refluxed to suppress the scattering of bromine. The mixed solution was continuously stirred in such a stirring tank, allowed to stay in the stirring tank for about 5 minutes, and then allowed to flow out of an overflow port of the stirring tank.

This reaction solution was treated in the same manner as in Example 50 to obtain 1.8 g of a reaction product. The product obtained in the same manner as in Example 50 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be bis {3,5-dibromo-4- (2,3-dibromo-2-). It was confirmed to be methylpropyloxy) phenyl @ methane. The bromine compound had a purity of 92.0% and a bromine content of 67.0% (theoretical value: 67.7%).

Example 55 A mixed solvent solution of 11.3 kg of (3,3 ', 5,5'-tetrabromo-4,4'-diallyloxy) biphenyl in methylene chloride and 1,4-dioxane (methylene chloride /
30 kg of 1,4-dioxane = 70/30 weight ratio was adjusted (the specific gravity of the solution was 1.35, and the water content was 250 pp.
m).

In a static mixer similar to that used in Example 50, the adjusted mixed solvent solution was added at a rate of 140.0 g / sec (103.7 mL / sec), and bromine was added at a rate of 28.8 g / sec ( 9.3 mL / sec), that is, continuously introduced into the static mixer so that the flow rate of the mixed solution was 226 cm / sec, and mixed (residence time in this static mixer was 0.18. Second), the mixed solution derived from the static mixer was charged into a 20-L stirring tank equipped with a condenser. In this stirring tank,
The reaction heat was radiated, and the vaporized vapor was refluxed to suppress the scattering of bromine. In such a stirring tank,
Subsequently, the mixed solution was stirred and retained in the stirring tank for about 3 minutes, and then was discharged from the overflow port of the stirring tank.

This reaction solution was treated in the same manner as in Example 50 to obtain 1.5 g of a reaction product. The product obtained in the same manner as in Example 50 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was identified as {3,3 ′, 5,5′-tetrabromo-4,4 ′-( 2,3-dibromo-propyloxy)｝ biphenyl was confirmed. The bromine compound had a purity of 93.5% and a bromine content of 70.0% (theoretical value: 70.9%).

Example 56 Bis {(3,5-dibromo-4-allyloxy)
40 kg of a methylene chloride solution containing 14.8 kg of phenyl disulfone was prepared (specific gravity of the solution was 1.47, water content was 6).
00 ppm).

In a static mixer similar to that used in Example 51, the adjusted methylene chloride solution was added at a rate of 99.3 g / sec (67.6 mL / sec), and bromine was added at a rate of 28.8 g / sec ( 9.3 mL / sec), that is, continuously introduced into the static mixer so that the flow rate of the mixed solution was 154 cm / sec, and after mixing (residence time in this static mixer was 0.13 Seconds), the mixed solution derived from the static mixer was charged into a 15-L stirring tank equipped with a condenser. In this stirring tank,
The reaction heat was radiated, and the vaporized vapor was refluxed to suppress the scattering of bromine. In such a stirring tank,
Subsequently, the mixed solution was stirred and retained in the stirring tank for about 3 minutes, and then was discharged from the overflow port of the stirring tank.

This reaction solution was treated in the same manner as in Example 50 to obtain 1.5 g of a reaction product. The product obtained in the same manner as in Example 50 was analyzed using ¹ H-NMR and FT-IR. As a result, the product was identified as {3,3 ′, 5,5′-tetrabromo-4,4 ′-( 2,3-dibromo-propyloxy)} sulfone. The bromine compound had a purity of 91.0% and a bromine content of 63.9% (theoretical 66.2%). Table 11 shows the results of Examples 50 to 56.

[0258]

[Table 11]

Preparation Example 1 In a 10-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,2-bis {(3,5
-Dibromo-4-allyloxy) phenyl} propane 2
700 g (4.33 mol) and 4600 g of methylene chloride dehydrated with synthetic zeolite were added and dissolved. While stirring this solution and refluxing methylene chloride at a temperature of 39 to 41 ° C., 1394 g of bromine (8.72 mol
1) was dropped from the dropping funnel in 8 minutes. After the completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 39 to 41 ° C. for 30 minutes while refluxing methylene chloride, thereby completing the bromine addition reaction.
From the reaction solution, 10 mL is collected with a whole pipette,
3.68 g of residual bromine in the bromine compound solution measured
/ L.

Preparation Example 2 In a 10-L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 2,2-bis {(3,5
-Dibromo-4-allyloxy) phenyl} propane 2
700 g (4.33 mol) and 460 g of chlorobenzene dehydrated with a synthetic zeolite were added and dissolved. While stirring the solution, at a temperature of 15 ° C., 1394 g of bromine
(8.72 mol) was dropped from the dropping funnel in 120 minutes. After the completion of the dropwise addition, the reaction solution was continuously stirred at a temperature of 15 ° C. for 30 minutes to complete the bromine addition reaction. From the reaction solution, 10 mL was collected with a whole pipette, and the residual bromine in the bromine compound solution was measured. As a result, it was 3.60 g / L.

Preparation Example 3 In Preparation Example 1, 2,2-bis {(3,5-dibromo-
Instead of 2700 g of 4-allyloxy) phenyl {propane, 2820 g of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (4.3
3 mol), a bromination reaction was carried out in the same manner as in Preparation Example 1, and the residual bromine in the bromine compound solution was measured. The result was 3.05 g / L.

Preparation Example 4 In Preparation Example 1, 2,2-bis {(3,5-dibromo-
The bromination reaction was carried out in the same manner as in Preparation Example 1, except that bis (3,5-dibromo-4-allyloxy) phenyl} methane (2580 g, 4.33 mol) was used instead of 2,700 g of 4-allyloxy) phenyl} propane. And the residual bromine in the bromine compound solution was measured. As a result, 3.05 g /
L.

Example 57 To 328 g of the bromine compound solution obtained in Preparation Example 1, 15.
12.5 g of a 6% by weight aqueous sodium bisulfite solution (3.7 mol of sodium hydrogen sulfite per mol of bromine) was added, and 3.8 g of a 25% by weight aqueous sodium hydroxide solution (1 mol of bromine per mol) was immediately added. (4.7 mol of sodium hydroxide), and 300 g of water so that the weight ratio between the methylene chloride phase and the aqueous phase becomes approximately 1: 1.
For 30 minutes. After completion of the stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, 100 mL of the reduced and neutralized methylene chloride phase was taken, and about 90% of methylene chloride was evaporated and removed from the methylene chloride phase, and 250 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This blocky solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain 114.7 g of a product.

When the obtained product was analyzed by ¹ H-NMR, a signal derived from —CHBr— was found at 4.51 to 4.53 ppm, and a signal derived from —CH ₂ Br was found at 3.94 to 4.09 ppm. Was done. From FT-IR analysis,-
O-CH ₂ -absorption was observed, and it was confirmed that no allyl group absorption was observed. From the above analysis results, the product is
It was confirmed that the substance was 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. 1 g of this bromine compound is added to 10 g of water,
After stirring at 0 ° C. for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 58 In Example 57, 12.5 g of a 15.6% by weight aqueous sodium bisulfite solution was replaced by 24.5 g (7.3 moles of sodium bisulfite per mole of bromine), and 25% by weight of Reduction and neutralization were carried out in the same manner as in Example 57, except that 3.8 g of the aqueous sodium hydroxide solution was replaced with 13.1 g (16.3 mol of sodium hydroxide per mol of bromine). The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,2
3-Dibromopropyloxy) phenyl} propane was obtained. After adding 1 g of this bromine compound to 10 g of water and stirring at 20 ° C. for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 59 In Example 57, 12.5 g of a 15.6% by weight aqueous sodium bisulfite solution was replaced with 9.7 g of a 15.6% by weight aqueous oxalic acid solution (3.3 moles of oxalic acid per mole of bromine). ), Except that reduction and neutralization were performed in the same manner as in Example 57. The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,2
3-Dibromopropyloxy) phenyl} propane was obtained. After adding 1 g of this bromine compound to 10 g of water and stirring at 20 ° C. for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 60 In Example 57, 12.5 g of a 15.6% by weight aqueous solution of sodium bisulfite was replaced by 7.1 g of a 15.6% by weight aqueous solution of sodium nitrite (3 moles of sodium nitrite per mole of bromine. Reduction and neutralization treatment in the same manner as in Example 57 except for changing to 2 mol). The methylene chloride phase and the aqueous phase were separated, the aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, in the same manner as in Example 57, 2,2-bis {3,5-dibromo-4- (2,2
3-Dibromopropyloxy) phenyl} propane was obtained. After adding 1 g of this bromine compound to 10 g of water and stirring at 20 ° C. for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 61 To 328 g of the bromine compound solution obtained in Preparation Example 2, 15.
12.5 g of a 6% by weight aqueous sodium bisulfite solution (3.0 mol of sodium bisulfite per mol of bromine) was added, and 3.8 g of a 25% by weight aqueous sodium hydroxide solution (1 mol of bromine per mol) was immediately added. 3.9 mol of sodium hydroxide), and 300 g of water so that the weight ratio of the chlorobenzene phase to the aqueous phase becomes approximately 1: 1.
Stirring was performed at 30 ° C. for 30 minutes. After completion of the stirring, the chlorobenzene phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the chlorobenzene phase, and the mixture was stirred and washed for 15 minutes.
The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, 100 mL of the reduced and neutralized chlorobenzene phase was taken, and about 90% of chlorobenzene was evaporated and removed from the chlorobenzene phase, and 250 mL of methanol was added thereto to precipitate a reaction product. The lump solid was removed by filtration. This massive solid was pulverized in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. . After adding 1 g of this bromine compound to 10 g of water and stirring at 20 ° C. for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 62 To 324 g of the bromine compound solution obtained in Preparation Example 3, 15.
13.0 g of a 6% by weight aqueous sodium bisulfite solution (4.7 moles of sodium hydrogen sulfite per mole of bromine) was added, and immediately 4.0 g of a 25% by weight aqueous solution of sodium hydroxide (1 mole of bromine) was added. Sodium hydroxide (6.1 mol), and water (300 g) so that the weight ratio of the methylene chloride phase to the aqueous phase becomes approximately 1: 1.
For 30 minutes. After completion of the stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, 100 mL of the reduced and neutralized methylene chloride phase was taken, and about 90% of methylene chloride was evaporated and removed from the methylene chloride phase, and 250 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This lump solid was crushed in a mortar, dried at 80 ° C. for 3 hours under reduced pressure of 5 mmHg,
2,2-bis {3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl} propane was obtained. 1 g of this bromine compound is added to 10 g of water,
After stirring for 24 hours, the bromine compound was filtered, and the bromine concentration in the aqueous phase was measured. As a result, no bromine was detected.

Example 63 To 328 g of the bromine compound solution obtained in Preparation Example 4, 15.
12.5 g of a 6% by weight aqueous sodium bisulfite solution (4.5 moles of sodium hydrogen sulfite per mole of bromine) was added, and immediately 3.9 g of a 25% by weight aqueous solution of sodium hydroxide (1 mole of bromine) was added. 5.8 mol of sodium hydroxide), and 300 g of water so that the weight ratio between the methylene chloride phase and the aqueous phase becomes approximately 1: 1.
For 30 minutes. After completion of the stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 100 mL of water was added to the methylene chloride phase, and the mixture was stirred and washed for 15 minutes. The pH of the aqueous phase was 7.2, and no bromine was detected in both phases.

Next, 100 mL of the reduced and neutralized methylene chloride phase was taken, and about 90% of methylene chloride was evaporated and removed from the methylene chloride phase, and 250 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid was crushed in a mortar and dried under reduced pressure at 5 mmHg at 80 ° C. for 3 hours to obtain bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} methane. 1 g of this bromine compound
Was added to 10 g of water, and the mixture was stirred at 20 ° C. for 24 hours. Then, the bromine compound was filtered, and the bromine concentration of the aqueous phase was measured. As a result, no bromine was detected.

Example 64 The methylene chloride solution prepared in Preparation Example 1 was added to a static mixer (cross-sectional area: 0.5 cm ² ) having an internal volume of 20 cm ³ and consisting of 12 elements at a rate of 10.7 g / sec (7.2 m ² ).
L / sec) and an aqueous solution of 15.6% by weight of sodium bisulfite were added at a rate of 0.4 g / sec (0.38 mL / sec), that is, a static mixer so that the flow rate of the mixed solution was 15.3 cm / sec. (Residence time in this static mixer is 2.6 seconds, 3.7 mol of sodium bisulfite per mol of bromine).
Mol), and was charged into a stirring tank having a bottom opening valve at the bottom of a volume of 30 L. The mixed solution was continuously stirred in the stirring tank, and after being kept in the stirring tank for about 10 minutes, a part was taken out from the bottom. When the bromine concentration in the methylene chloride solution phase was measured, no bromine was detected.

Next, 14 L of the reduced mixed solution taken out from the bottom of the stirring tank was added to 3000 g of a 2.5% by weight aqueous solution of sodium hydroxide with vigorous stirring (5 moles of sodium hydroxide per mole of bromine). .9 mol). This stirring was performed for 20 minutes. After completion of the stirring, the methylene chloride phase and the aqueous phase were separated. The aqueous phase was removed, 2000 g of pure water was added to the methylene chloride phase, and the mixture was stirred and washed for 20 minutes. The time required to complete the reduction and neutralization reactions was about 1 hour.

Example 65 Instead of the static mixer having an internal volume of 20 cm ³ having 12 elements and having a cross-sectional area of 0.5 cm ^{2, a} static mixer having an internal volume of 30 cm ³ having 18 elements and having a cross-sectional area of 0.5 was used. 0.5 cm ² ), the concentration of the aqueous solution of sodium bisulfite was 5.2% by weight, and the addition rate was 0.8 g / sec (0.75 mL / sec). (The flow rate of the mixed solution was 15.9 cm / sec, the residence time in the static mixer was 3.8 seconds, and 2.5 mol of sodium bisulfite per mol of bromine.) ). When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

EXAMPLE 66 Instead of the static mixer having an internal volume of 20 cm ³ having 12 elements and having a cross-sectional area of 0.5 cm ^{2, a} static mixer having an internal volume of 30 cm ³ having 18 elements and having a cross-sectional area of 0.5 was used. 0.5 cm ² ) and the methylene chloride solution was added at a rate of 26.9 g / sec (18.2 mL / sec).
And the addition rate of the aqueous solution of sodium hydrogen sulfite is 1.
Example 1 except that it was 04 g / sec (0.95 mL / sec)
(The flow rate of the mixed solution was 38.3.)
cm / sec and the residence time in the static mixer is 1.5 seconds, 3.7 mol of sodium bisulfite per mol of bromine). When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

Example 67 The procedure of Example 64 was repeated, except that the addition rate of the aqueous solution of sodium bisulfite was changed to 0.8 g / sec (0.75 mL / sec) (mixed solution). Is 16.0 cm / sec, the residence time in the static mixer is 2.6 seconds, and 7.4 mol of sodium bisulfite per mol of bromine). When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

Example 68 In Example 64, the methylene chloride solution prepared in Preparation Example 1 was replaced with the chlorobenzene solution prepared in Preparation Example 2,
The same operation as in Example 1 was performed except that the addition rate was 10.9 g / sec (9.9 mL / sec) (the flow rate of the mixed solution was 20.7 cm / sec, and Is 1.9 seconds and 3.0 moles of sodium bisulfite per mole of bromine). When the bromine concentration in the chlorobenzene solution phase after the reduction reaction was measured in the same manner as in Example 1, no bromine was detected.

Example 69 The procedure of Example 64 was repeated except that the methylene chloride solution prepared in Preparation Example 1 was replaced with the methylene chloride solution prepared in Preparation Example 4 (flow rate of mixed solution). Is 15.2 cm / sec, the residence time in the static mixer is 2.7 seconds, 3.7 mol of sodium bisulfite per mol of bromine). When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

Example 70 In Example 64, the addition rate of the methylene chloride solution was 5.
4 g / sec (3.6 mL / sec), and the addition rate of the aqueous solution of sodium bisulfite was 0.2 g / sec (0.19 mL / sec).
The procedure was the same as in Example 1 except that the flow rate of the mixed solution was 7.6 cm / sec, the residence time in the static mixer was 5.3 seconds, and 1 mol of bromine was used. 3.7 mol of sodium bisulfite based on When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

Example 71 In Example 64, a 15.6% by weight aqueous solution of sodium dithionite was used in place of the aqueous solution of sodium bisulfite, and the addition rate was 0.4 g / sec (0.38 m
L / sec), except that the flow rate of the mixed solution was 15.2 cm / sec, the residence time in the static mixer was 2.6 sec. 1
2.5 moles of sodium dithionite per mole). When the bromine concentration of the methylene chloride solution phase after the reduction reaction was measured in the same manner as in Example 64, no bromine was detected.

[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

FIG. 2 shows an example of a reactor for performing a bromination reaction in the present invention.

FIG. 3 shows another example of a reaction apparatus for performing a bromination reaction in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Input port of raw material compound solution 2 Input port of bromine or bromine solution 3 Stirrer blade 4 Condenser 5 Thermometer 6 Pump 7 Input port of circulating fluid 8 Input port of reaction solution 9 Reaction solution

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 315/04 C07C 315/04 317/20 317/20 317/22 317/22 319/20 319/20 323 / 18 323/18 C09K 21/08 C09K 21/08 (72) Inventor Yasuhiro Shimizu 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Inside Teijin Chemicals Co., Ltd. (72) Inventor Seiichi Tanabe 1 Uchisaiwaicho, Chiyoda-ku, Tokyo (2-2) Inventor Haruhisa Hoshimi 1-2-2 Uchisaiwai-cho, Chiyoda-ku, Tokyo F-term (reference) 4H006 AA02 AA03 AB99 AC30 BB12 BB49 BC10 BE53 GP20 GP22 TA02 TA04 TB13 TB14 4H028 AA28

Claims (18)

[Claims] 1. A method for producing a bromine compound represented by the following general formula (2) by reacting a compound having an aliphatic unsaturated bond represented by the following general formula (1) with bromine,
A process for producing a bromine compound, comprising conducting the reaction in the presence of a solvent inert to the reaction, and removing a substantial amount of the heat of reaction out of the reaction system by the solvent or the heat of vaporization of bromine. R ¹ —O—Ar ¹ —Y—Ar ² —O—R ² (1) (wherein, Ar ¹ and Ar ² may be the same or different and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and these hydrocarbon groups may be substituted by at least one halogen atom; Y is a saturated hydrocarbon group having 1 to 6 carbon atoms, sulfone A sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms or a single bond; R ¹ and R ² may be the same or different, and have 2 carbon atoms having at least one aliphatic unsaturated group. And R 11 represents a hydrocarbon group of any one of R ¹ and R ² , and ^one of R ¹ and R ² may have a part of the unsaturated group added by a halogen atom.) R ³ —O—Ar ¹ —Y—Ar ^{2 -O-R 4 (2)} ( wherein, Ar ^1, Ar ² and Y are Means the same thing as defined in serial formula (1) .R ³ and R ⁴ are each unsaturated group in R ¹ and R ² in the general formula (1) means a saturated group by a bromine atom. ) 2. The method for producing a bromine compound according to claim 1, wherein a substantial amount of heat of reaction is removed to the outside of the reaction system by heat of vaporization of the solvent. 3. The method for producing a bromine compound according to claim 1, wherein said solvent has a normal pressure boiling point of 0 to 100 ° C. 4. The method according to claim 1, wherein the solvent is a halogenated hydrocarbon. 5. The method according to claim 1, wherein the solvent is a compound represented by the general formula (1), wherein one of the unsaturated groups in the compound is 2 to 10 or less.
The process for producing a bromine compound according to claim 1, which is used in an amount of 00 molecules. 6. The method for producing a bromine compound according to claim 1, wherein 1 to 5 molecules of bromine are used per one unsaturated group in the compound represented by the general formula (1). 7. The method for producing a bromine compound according to claim 1, wherein the reaction is carried out at a temperature in the range of 0 to 60 ° C. 8. The following general formula (1): R ⁵ — (OH) _n (3) wherein R ⁵ is an n-valent aliphatic group having 1 to 6 carbon atoms, and n is 1 to 4 The method for producing a bromine compound according to claim 1, wherein an alcohol represented by an integer is further added to the reaction system. 9. The alcohol is used in an amount corresponding to the number of hydrogen groups of 0.5 to 20 per 100 unsaturated groups in the compound represented by the general formula (1). The method for producing a bromine compound according to claim 8, wherein 10. The method according to claim 1, wherein the reaction is carried out on the compound having an aliphatic unsaturated bond in the presence of water of 10 molecules or less per 100 unsaturated groups of the compound. Production method. 11. A method for producing a bromine compound represented by the general formula (2) by reacting a compound having an aliphatic unsaturated bond represented by the general formula (1) with bromine. The compound of the formula (1), bromine and the solvent inert to the reaction are continuously fed into the reactor separately or as a mixture of any combination,
To the compound represented by the general formula (1), bromine is supplied in an amount of 1 to 5 molecules per unsaturated group in the compound, and the substantial amount of heat of reaction is reduced in the reactor. The reaction is carried out while removing the solvent or the heat of vaporization of bromine while removing the reaction mixture, the reaction mixture is taken out of the reactor, and then the bromine compound represented by the general formula (2) is recovered from the reaction mixture. Continuous manufacturing method. 12. The bromine according to claim 11, wherein the compound having an aliphatic unsaturated group and bromine are continuously fed into a reactor through a flow mixer as a mixed liquid stream together with at least one part of a solvent, if necessary. A method for continuously producing a compound. 13. The continuous production method of a bromine compound according to claim 12, wherein the flow rate of the liquid stream in the flow mixer is 15 to 500 cm / sec. 14. The continuous method for producing a bromine compound according to claim 12, wherein the residence time of the liquid stream in the flow mixer is 0.01 to 180 seconds. 15. The continuous method for producing a bromine compound according to claim 12, wherein the flow mixer is a static mixer. 16. The method according to claim 16, wherein the flow mixer has 4 to 4 elements.
13. The continuous production method of a bromine compound according to claim 12, which is a static mixer having 20. 17. The following general formula wherein the content of the hydroxybromine compound represented by the following general formula (4) is 0.02 mol or less per 1 mol of the bromine compound represented by the following general formula (2): A bromine compound represented by (2). R ³ —O—Ar ¹ —Y—Ar ² —O—R ⁴ (2) (wherein, Ar ¹ and Ar ² may be the same or different and have an aromatic hydrocarbon group having 5 to 16 carbon atoms or Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and these hydrocarbon groups may be substituted by at least one halogen atom; Y is 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 bond;
May be the same or different and have 2 to 11 carbon atoms
Wherein a bromine atom is added to the hydrocarbon group. ) (In the formula, Ar ¹ , Ar ² and Y have the same meanings as defined in the general 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, and (p +
q) represents 1 or more, preferably an integer of 2 to 10, s and t each represent an integer of 0 to 5, and (s + t) represents 1
Above, preferably an integer of 1 to 5 is shown. ) 18. A bromine compound substantially represented by the general formula (2), wherein the hydroxybromine compound represented by the general formula (4) is 0.02 mol per 1 mol of the bromine compound. Flame retardant contained below.