JPH11171813A - Production of bromine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject high-purity compound having excellent heat stability, by reacting an aliphatic unsaturated bond-containing compound with bromine in the presence of a specific hydroxyl group-containing compound. SOLUTION: This aliphatic unsaturated bond-containing compound of formula I (X is a halogen; (m) and (n) are each 1-6; Ar<1> and Ar<2> are each a 5-16C aromatic hydrocarbon or a 5-12C saturated alicyclic hydrocarbon; Y is sulfido, ketone or the like; R<1> and R<2> are each an aliphatic unsaturated group-containing 2-11C hydrocarbon) or its solution in a solvent is brominated with bromine or a bromine solution. In the bromination, the reaction is carried out by using a hydroxyl group-containing compound of the formula; R<5> -(OH)u (R<5> is a mono- to tetrafunctional aliphatic group; (u) is 1-4) so as to give 0.5-10 hydroxyl groups of the hydroxyl group-containing compound based on 100 unsaturated groups of the compound of formula I to obtain the objective compound of formula II (R<3> and R<4> are each obtained by adding a bromine atom to at least one aliphatic unsaturated group of R<1> and R<2> ). Methanol or the like is preferable as the compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Generally, a bromination reaction to an aliphatic unsaturated group is a reaction that is frequently employed in synthesizing a brominated derivative in the field of organic chemistry. Then, due to the intensity of the reaction, usually, an operation of adding bromine to a solution of the compound containing an aliphatic unsaturated group is performed,
Further, in order to remove reaction heat generated during the bromination reaction, a method of cooling the reaction system and controlling the reaction temperature has been used.

[0003] For example, Japanese Patent Publication No. 49-39655 describes a method for producing β, γ-dibromopropylbenzene. Bromine is added to an allylbenzene solution at a low temperature to cause a 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 shown that the bromination is carried out in a halogenated hydrocarbon solvent, and the examples specifically show a method of adding bromine under cooling at a temperature of about 20 ° C.

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

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-
For the reaction of bromine with allyloxy) phenyl-propane or the like, a method is described in which 156 g of bromine is dropped at a reaction temperature of 10 to 20 ° C. over 1 hour.

Further, in Japanese Patent Application Laid-Open No. Hei 7-316087, as a specific example, the reaction temperature of a 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane in methylene chloride solution is controlled by a condenser. A method of dropping 469 g of bromine over 1 hour while controlling the temperature at 24 to 27 ° C. is disclosed.

Japanese Patent Publication No. 50-23693 discloses, as a specific example, the bromination of bis {(3,5-dibromo-4-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 dropped at 39 ° C. or 40 ° C. over 1 hour to a methylene chloride solution of the compound, and the latter is bromine at 35 to 39 ° C. For 1.5 hours.

However, in these methods,
At the time of such bromination reaction, along with the production of the intended bromine compound, the generation of by-products also occurs, so that the obtained bromine compound has low purity and insufficient thermal stability, and has high purity and thermal stability. A production method for obtaining an excellent bromine compound is desired.

[0011]

SUMMARY OF THE INVENTION The present inventor has provided a method for producing a bromine compound having high purity and excellent heat stability by reacting a compound having an aliphatic unsaturated bond with bromine. As a result of intensive studies for the purpose, during the bromination reaction, a solution of a compound having an aliphatic unsaturated bond or a compound having the aliphatic unsaturated bond in a solvent inert to bromine and bromine or bromine It has been found that a side reaction occurs due to moisture contained in the mixed solution with the solution, and that such water-derived by-products lower the thermal stability of the bromine compound.

[0012] However, although the amount of water in the mixed solution can be reduced to some extent, the thermal stability of the obtained bromine compound is still insufficient, and in order to reduce the amount of water, there are restrictions on equipment and operation. Many were inconvenient.

Therefore, as a result of further study, it was found that a compound having an aliphatic unsaturated bond or a solution in which the compound having an aliphatic unsaturated bond was dissolved in a solvent inert to bromine was converted into bromine or a bromine solution. And then brominated,
And, at the time of such a bromination reaction, using a specific compound having a hydroxyl group, by a production method of reacting, with high purity,
Finding that a bromine compound with excellent heat stability can be obtained,
The present invention has been reached.

[0014]

That is, according to the present invention, a compound having an aliphatic unsaturated bond represented by the following formula (1) or a compound having the aliphatic unsaturated bond is inert to bromine. A solution dissolved in a solvent is added to bromine or a bromine solution and subjected to a bromination reaction. In the bromination reaction, the compound having an aliphatic unsaturated bond is added to the compound having 100 unsaturated groups per 100 And a compound having a hydroxyl group represented by the following formula (3), wherein the number of hydroxyl groups is 0.5 to
There is provided a method for producing a bromine compound represented by the following formula (2), characterized in that the reaction is carried out by using an amount corresponding to 10 compounds.

[0015]

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(Wherein X is a halogen atom, m and n are integers of 1 to 6, Ar ¹ and Ar ² may be the same or different, and may be an aromatic hydrocarbon group having 5 to 16 carbon atoms or carbon atom). Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms, and a single bond. R ¹ and R ² each have at least one aliphatic unsaturated group and have 2 carbon atoms.
To 11 hydrocarbon groups. )

[0017]

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(Where X, m, n, Ar ¹ , Ar ² ,
Y is the same as in the above formula (1), and R ³ and R ⁴ are those in which at least one of the aliphatic unsaturated groups of R ¹ and R ^{2 in} the above formula (1) additionally contains bromine. is there. )

[0019]

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(Wherein R ⁵ is a C 1 -C 4 valence)
6 is an aliphatic group, and u represents an integer of 1 to 4. )

The compound having an aliphatic unsaturated bond used in the present invention is represented by the above formula (1), wherein X is a halogen atom, preferably bromine, and m and n are integers of 1 to 6, preferably Is an integer of 2 to 4, Ar ¹ and Ar ² may be the same or different, and are an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, preferably Is a phenyl group, a tolyl group, a xylyl group or a naphthyl group. Y is one selected from 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 and a single bond, and is preferably methylene, isopropylidene, cyclohexylidene. R ¹ and R ² are each ^one selected from den, sulfone, sulfide, ketone, and a single bond, and each of R ¹ and R ² has ² to 1 carbon atoms having at least one aliphatic unsaturated group.
1 hydrocarbon group.

Specific examples of such compounds having an aliphatic unsaturated bond include 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and 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; and among others, 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 is more preferred, and 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is particularly preferred.

In the present invention, a solution in which the compound having an aliphatic unsaturated bond or the compound having an aliphatic unsaturated bond is dissolved in a solvent inert to bromine is used. The solvent used to dissolve the compound having an aliphatic unsaturated bond needs to be substantially inert to bromine. Such a solvent is preferably as high as possible in solubility for a compound having an aliphatic unsaturated bond, but may be in a partially dissolved state. That is, it is preferable that the bromine compound produced by the bromination reaction of the compound having an aliphatic unsaturated bond is soluble in the solvent.

Examples of such a solvent include halogen-containing hydrocarbon compounds such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, chlorobenzene and acetone chloride, diethyl ether, and ethyl isopropyl. Ether hydrocarbon compounds such as ether, tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, carbon disulfide, pentane and the like, among which methylene chloride, chloroform and dioxane are preferable, and methylene chloride is particularly preferable. Is preferably used. These solvents are used alone or in combination of two or more.

In the present invention, bromine or a bromine solution is used. As a solvent for use in the bromine solution, the same solvent as that used for dissolving the compound having an aliphatic unsaturated bond is used.

In the present invention, a compound having an aliphatic unsaturated bond or a solution in which a compound having an aliphatic unsaturated bond is dissolved in a solvent inert to bromine is added to bromine or a bromine solution, and the aliphatic unsaturated bond is added. A compound having a saturated bond is reacted with bromine. By employing this method, the compound having an aliphatic unsaturated bond to be added comes into contact with and reacts with bromine immediately after being added. It is considered that a side reaction with the compound is suppressed and a high-purity bromine compound can be obtained.

Further, in the method of the present invention, as described above, a solution having a compound having an aliphatic unsaturated bond or a compound having an aliphatic unsaturated bond dissolved in a solvent inert to bromine is treated with bromine or bromine. When reacting a compound having an aliphatic unsaturated bond with bromine by adding it to a bromine solution, it is necessary to use a compound having a hydroxyl group represented by the above formula (3). Such a compound having a specific hydroxyl group is blended in a solution of a compound having an aliphatic unsaturated bond or bromine or a bromine solution, and by allowing the compound having the specific hydroxyl group to exist in a reaction solution, The reaction between the intermediate produced by the reaction and the aliphatic unsaturated group of the compound having an aliphatic unsaturated bond is suppressed,
Further, a by-product formed by reacting the intermediate formed by the reaction of the compound having a hydroxyl group with bromine with the aliphatic unsaturated group of the compound having an aliphatic unsaturated bond is a thermostable compound of the bromine compound. The resulting bromine compound has good thermal stability since it does not adversely affect the properties.

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

The compound having a hydroxyl group is different from the compound having an aliphatic unsaturated bond in that the unsaturated group 10
An amount corresponding to 0.5 to 10, preferably 0.8 to 8, and more preferably 1 to 5 hydroxyl groups is used per 0. When the amount of the compound having a hydroxyl group is less than the amount of the compound having an aliphatic unsaturated bond and the number of hydroxyl groups is less than 0.5 per 100 units of the unsaturated group, water and bromine are used. When the reaction between the intermediate produced by the reaction with the compound having an aliphatic unsaturated bond and the compound having an aliphatic unsaturated bond easily proceeds, the thermal stability of the resulting bromine compound decreases, which is not preferable. An intermediate produced by the reaction of the compound having a hydroxyl group with bromine has an increased amount of by-products produced by reacting with a compound having an aliphatic unsaturated bond, and the purity of the obtained bromine compound is insufficient. Further, such a bromine compound is not preferable because it has a bad influence on the flame retardancy of the resin composition in which the resin composition is blended with the resin as a flame retardant.

In the present invention, a method of removing the heat of bromination by the heat of vaporization of a solvent or bromine at the time of the bromination reaction can be adopted. To liquefy, and return to the reaction system again, that is, a refluxing method.

In the production method of the present invention, a compound having an aliphatic unsaturated bond or a compound having an aliphatic unsaturated bond is placed in a reaction vessel filled with bromine or a bromine solution in a solvent inert to bromine. A method of completing a bromination reaction by adding a certain amount of a dissolved solution is usually used. At this time, a reaction solution may be appropriately drawn out from a reaction tank, and a part of the drawn-out reaction solution may be circulated.

The reaction temperature in the bromination reaction of the present invention is as follows:
The temperature is preferably −20 ° C. or higher, more preferably 5 ° C. or higher, and the bromination reaction is not limited to normal pressure, and can be performed under increased or reduced pressure.

The amount of bromine used in the method of the present invention is
In order to obtain a desired bromine compound, a sufficient molar ratio is required for the compound having an aliphatic unsaturated bond, and 2 mol to 10 mol of bromine is used per 1 mol of the compound having the aliphatic unsaturated bond. A molar range is preferred. The amount of bromine is determined by the structure of the intended bromine compound,
When a compound having two aliphatic unsaturated bonds is used as represented by bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 1 mole of the compound is A range of 2 to 3 moles of bromine is preferred.

In the bromination reaction of the present invention, as described above, when a compound having an aliphatic unsaturated bond or a solution of a compound having an aliphatic unsaturated bond is added to bromine or a bromine solution to be reacted, The presence of a compound having a hydroxyl group in the reaction solution suppresses the generation of by-products due to moisture. However, if the amount of water present in the reaction solution is too large, a large amount of the compound having the hydroxyl group is used in order to suppress a side reaction due to moisture, and therefore, the compound having the hydroxyl group is used as described above. Intermediates generated by the reaction between the compound and bromine will produce a large amount of by-products that have reacted with the compound having an aliphatic unsaturated bond, and the purity of the resulting bromine compound will be insufficient. Has 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. The amount corresponding to the number of water molecules is preferably 10 or less per 100 unsaturated groups of the compound.
An amount corresponding to 10 is more preferable, and an amount corresponding to 0.05 to 5 is more preferable. Such a water content is measured by the Karl Fischer method.

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

After the above bromination reaction, excess bromine is usually reduced with a reducing agent.
The excess bromine can be recovered by distillation together with the solvent and used for bromination in the next step.

As the reducing agent, various reagents used in a usual reduction reaction are used. Specifically, sodium bisulfite, sodium hyposulfite, sodium sulfite, hydroxylamine sulfate, tin, stannous oxide, hydrazine And propylene oxide are preferably used.

The bromine compound produced by the reaction of the present invention is represented by the above formula (2) and comprises X, m, n, Ar ¹ , A
r ² and Y are the same as those described in the above formula (1),
In R ³ and R ⁴ , at least one of the aliphatic unsaturated groups of R ¹ and R ^{2 in} the above formula (1) additionally contains bromine. Such a bromine compound is useful as a flame retardant for resins, particularly polyethylene, a polyolefin resin such as a polypropylene resin, an ABS resin, a polystyrene resin,
It is suitable as a flame retardant for rubber-modified polystyrene (HIPS) resin.

The bromine compound obtained by the bromination reaction is recovered by an appropriate method well known to those skilled in the art, for example, precipitation with a poor solvent. Further, the obtained bromine compound can be identified by a usual analysis method, for example, analysis of ¹ H-NMR spectrum and IR spectrum.

[0040]

The present invention will be described below in detail with reference to examples. The analysis of purity, impurities derived from water, impurities derived from the hydroxyl group-containing compound, analysis of water content, and measurement of the inclination angle were performed according to the following methods. Further, the compound containing a hydroxyl group used in the examples was purified by distillation in advance, added with molecular sieve 3A, and dehydrated.

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

(2) Analysis of Water Content Coulometric titration-type water measurement device (CA-06 manufactured by Mitsubishi Chemical Corporation)
) And by the Karl Fischer method.

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

Example 1 72.7 g (0.455 mol) of bromine was charged into a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel. In addition, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (0.216
mol) was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g of methanol (0.
A solution was prepared by adding 0,113 mol, the number of hydroxyl groups (2.6) per 100 aliphatic unsaturated groups. Next, the bromine in the reaction vessel is cooled to 2 ° C.
A methylene chloride solution of -bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped into bromine from a 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. The water content in the reaction solution was 200 ppm (the number of water molecules was 1.1 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, 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, the signal derived from —CHBr— was found to be 4.51 to 4.53 ppm, and the —CH ₂ Br was found to be 3.94 to 4.09 ppm.
Originated signals were observed. Further, from FT-IR analysis, it was confirmed that -O-CH ₂ -absorption was observed and no allyl group absorption was observed. From the above analysis results, the product was found to be mainly 2,2-bis {3,5-dibromo-4-
(2,3-Dibromopropyloxy) phenyl} propane was confirmed. This bromine compound has a purity of 9
6.7% and 2,2-bis {3,5-dibromo-4
The impurity derived from water is 0.002 to 1 mol of-(2,3-dibromopropyloxy) phenyl @ propane.
The impurity derived from 3 moles and methanol was 0.0155 mole. Further, the inclination angle of the bromine compound is 40 °.
Met.

Example 2 In Example 1, 0.36 g of ethanol (0.00783 m
ol, aliphatic unsaturated group A bromine addition reaction was carried out in the same manner as in Example 1, except that the number of hydroxyl groups per 100 aliphatic unsaturated groups was 1.8. The water content in this reaction solution was 210 ppm (100 aliphatic unsaturated groups).
1.2 water molecules per unit).

This reaction solution was subjected to the same operation 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 96.1%,
For 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. 0.0124 mol. The inclination angle of the bromine compound was 41 °.

Example 3 72.6 g (0.454 mol) of bromine and 230 g of methylene chloride were placed in a 1 L glass reactor equipped with a stirrer, condenser, thermometer and dropping funnel. In addition, 2,2-bis (3,
135 g (0.216 mol) of 5-dibromo-4-allyloxy) phenyl @ propane was added to 230 g of methylene chloride.
In ethanol and 0.36 g of ethanol (0.0078 g).
3 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups
8) was prepared. Next, the bromine solution in the reaction vessel is cooled to 2 ° C. and the 2,2-
A methylene chloride solution of bis {(3,5-dibromo-4-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 dropping, the reaction solution is added for 30 minutes.
The stirring was continued for another minute, and the addition reaction of bromine was completed. The water content in this reaction solution was 420 ppm (3.6 water molecules per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 was analyzed using ¹ H-NMR and FT-IR, and 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 an impurity derived from water is added 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 4 72.6 g (0.454 mol) of bromine and 230 g of methylene chloride were placed in a 1 L glass reactor equipped with a stirrer, condenser, thermometer and dropping funnel. In addition, 2,2-bis (3,
135 g (0.216 mol) of 5-dibromo-4-allyloxy) phenyl @ propane was added to 230 g of methylene chloride.
In ethanol and 0.36 g of ethanol (0.0078 g).
3 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups
8) was prepared. Next, a methylene chloride solution of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane is refluxed at a temperature of 39 to 41 ° C. while stirring the inside of the reaction vessel. Was added dropwise to the bromine solution from the dropping funnel over 10 minutes. After 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. The water content in this reaction solution was 420
ppm (the number of water molecules is 3.6 per 100 aliphatically unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 was analyzed using ¹ H-NMR and FT-IR, and 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 an impurity derived from water is contained in 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 5 In a 500 mL glass reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 72.6 g (0.454 mol) of bromine, 230 g of methylene chloride dehydrated with synthetic zeolite and ethanol were added. 0.36 g (0.00783 mol, the number of hydroxyl groups per 100 aliphatic unsaturated groups: 1.8) was added. Next, while stirring the inside of the reaction vessel and refluxing methylene chloride at a temperature of 39 to 41 ° C., 2,2-bis {(3,
135 g (0.216 mol) of 5-dibromo-4-allyloxy) phenyl @ propane was added to the bromine solution over 5 minutes. After the addition was completed, the reaction solution was continuously stirred at a temperature of 39 to 41 ° C. for 30 minutes while refluxing methylene chloride,
The bromine addition reaction was completed. The water content in this reaction solution was 210 ppm (the number of water molecules was 1.2 per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 was analyzed using ¹ H-NMR and FT-IR, and 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 an impurity derived from water is contained in 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0021 mol, and impurities derived from ethanol were 0.0135 mol.

Example 6 72.7 g (0.455 mol) of bromine was charged into a 1 L glass reaction vessel equipped with a stirrer, condenser, thermometer and dropping funnel. In addition, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (0.216 mo
1) methylene chloride 23 dehydrated with synthetic zeolite
0 g, and 0.36 g of i-propanol was added thereto.
(0.0060 mol, the number of hydroxyl groups per 100 aliphatic unsaturated groups: 1.4) was prepared. Next, the bromine in the reaction vessel was cooled to about 2 ° C.
A solution of 2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped into bromine from a dropping funnel over 60 minutes. At the end of dropping, the temperature of the reaction solution is 20
° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in the reaction solution was 200 ppm (the number of water molecules was 1.1 per 100 aliphatic unsaturated groups).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 was analyzed using ¹ H-NMR and FT-IR, and 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 an impurity derived from water is added 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 7 72.7 g (0.455 mol) of bromine was placed in a 1 L glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel. In addition, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane (0.216 mo
l) chloroform 61 dehydrated with synthetic zeolite
5 g, and methanol 0.54 g (0.01
A solution was prepared by adding 69 mol of the compound (several 3.9 hydroxyl groups per 100 aliphatic unsaturated groups). Next, the bromine in the reaction vessel is cooled to 2 ° C., and the 2,2-
A chloroform solution of bis {(3,5-dibromo-4-allyloxy) phenyl} propane was dropped into bromine from a 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. The water content in this reaction solution was 100 ppm (aliphatic unsaturated group 1
The number of water molecules is 1.1 per 00).

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, 200 g of ion-exchanged water was added, and after stirring, a chloroform layer was separated from this solution. About 90% of chloroform was evaporated and removed from the chloroform layer, and 500 mL of methanol was added thereto to precipitate a reaction product. The material was filtered to remove 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. As in Example 1, the obtained product was analyzed using ¹ H-NMR and FT-IR, and as a result, the product was found to be mainly 2,2-bis @ 3,3.
It was confirmed to be 5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. This bromine compound has a purity of 95.8% and is derived from water based on 1 mol of 2,2-bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} propane. Was 0.0022 mol, and impurities derived from methanol were 0.0155 mol.

Example 8 69.5 g (0.435 mol) of bromine was charged into a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel. In addition, 135 g of 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane (0.
207 mol) was dissolved in 230 g of methylene chloride dehydrated with synthetic zeolite, and 0.36 g of methanol was added thereto.
(0.0113 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups: 2.7) was prepared. Next, the bromine in the reaction vessel was cooled to about 2 ° C.
A solution of 2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane was dropped into bromine from a 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. The water content in this reaction solution was 190 ppm (aliphatic unsaturated group 10
1.1 number of water molecules per 0).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 was analyzed using ¹ H-NMR and FT-IR, and 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% and is 2,2-bis {3,5-dibromo-4- (2,3-
The amount of impurities derived from water is 0.002 per 1 mol of dibromo-2-methylpropyloxy) phenyl @ propane.
The impurity derived from 1 mol and methanol was 0.0212 mol.

Example 9 70.1 g (0.439 mol) of bromine was placed in a 500 mL glass reaction vessel equipped with a stirrer, a condenser, a thermometer and a dropping funnel. In addition, 135 g of bis {3,5-dibromo-4-allyloxy) phenyl} sulfone (0.209 mol
1) methylene chloride 23 dehydrated with synthetic zeolite
0 g, and 0.36 g of methanol (0.01 g
A solution was prepared by adding 13 mol of the compound (several 2.7 groups of hydroxyl groups per 100 aliphatic unsaturated groups). Next, the bromine in the reaction vessel was cooled to about 2 ° C.
A solution of -dibromo-4-allyloxy) phenyl} sulfone was dropped into bromine from a 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. The water content in this reaction solution is 180 ppm
(The number of water molecules per 100 aliphatically unsaturated groups: 1.
0).

The obtained reaction solution was subjected to the same operation as in Example 1 to obtain a white solid product. The product obtained in the same manner as in Example 1 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 amount of impurities derived from water is 0.0020 with respect to 1 mol of bis {3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl} sulfone. The impurities derived from mol and methanol are 0.1%.
0328 mol.

Example 10 A stirrer, a condenser,
In a 500 mL glass reaction vessel equipped with a thermometer and a dropping funnel, 76.2 g (0.477 mol) of bromine was charged. Further, 135 g (0.227 mol) of bis {3,5-dibromo-4-allyloxy) phenyl} methane was dissolved in 615 g of chloroform dehydrated with synthetic zeolite, and 1.13 g (0.015 g) of n-butanol was added thereto.
2. 7 mol, number of hydroxyl groups per 100 aliphatic unsaturated groups
5) was prepared. 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 dropping,
The reaction solution was continuously stirred for 30 minutes to complete the bromine addition reaction. The water content in this 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 7 to obtain a white solid product. As in Example 1, the obtained product was analyzed using ¹ H-NMR and FT-IR.
-Dibromo-4- (2,3-dibromopropyloxy)
It was confirmed to be 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 11] A stirring device, a condenser,
In a 1 L glass reaction vessel equipped with a thermometer and a dropping funnel, 77.9 g (0.487 mol) of bromine and 123 g of 1,4-dioxane dehydrated with a synthetic zeolite were placed. Also, (3,3 ', 5,5'-tetrabromo-
135 g of 4,4'-diallyloxy) biphenyl (0.
232 mol) was dehydrated with synthetic zeolite.
-Dissolved in 615 g of dioxane, and added with 1.13 g of n-butanol (0.0157 mol, aliphatic unsaturated group 10).
A solution was prepared by adding (number of hydroxyl groups: 3.4 per 0). Next, the bromine solution in the reaction vessel was set at about 22 ° C,
While stirring, (3,3 ', 5,5'-tetrabromo-
The solution of (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 complete the bromine addition reaction. The water content in this reaction solution was 120 ppm (number of water molecules per 100 aliphatic unsaturated groups: 1.4).

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, 100 g of ion-exchanged water was added, and after stirring, the 1,4-dioxane layer was separated from this solution.
%, 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. As in Example 1, the obtained product was analyzed using ¹ H-NMR and FT-IR. As a result, the product was found to be mainly {3,3 ′, 5,5′-tetrabromo-4,4 ′. −
(2,3-Dibromo-propyloxy)} biphenyl was confirmed. This bromine compound has a purity of 94.
6%, and {3,3 ′, 5,5′-tetrabromo-
Impurity derived from water is 0.0 to 1 mol of 4,4 '-(2,3-dibromo-propyloxy) @biphenyl.
018 mol, impurities derived from n-butanol are 0.0
254 mol.

Comparative Example 1 In a 1 L glass reactor equipped with a stirrer, condenser, thermometer and dropping funnel, 135 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was placed. (0.216mo
l) and methylene chloride (230 g) were dissolved therein (the water content in this solution was 500 ppm, and the number of water molecules was 2.4 per 100 aliphatic unsaturated groups). Next, while stirring the inside of the reaction vessel, at a temperature of 15 to 20 ° C., bromine 7
2.6 g (0.454 mol) was dropped from the dropping funnel over 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 1 to obtain 2,2-bis {3,5-dibromo-
4- (2,3-Dibromopropyloxy) phenyl} propane was obtained. This bromine compound has a purity of 84.8% and is 2,2-bis {3,5-dibromo-4- (2,3-
Impurity derived from water was 0.024 mol with respect to 1 mol of dibromopropyloxy) phenyl @ propane. Further, the inclination angle of the bromine compound is 78 °,
It was recognized that the bromine compound powder easily adhered to each other and had a problem in thermal stability.

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

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

According to the method of the present invention, when a compound having an aliphatic unsaturated bond or a solution thereof is added to bromine or a bromine solution to cause a bromination reaction, a compound having a specific hydroxyl group is used. As a result, a bromine compound having high purity and excellent heat stability can be obtained. Such a bromine compound is suitably used as a flame retardant for a resin, and its industrial effect is remarkable.

[Brief description of the drawings]

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

[Explanation of symbols]

 1 Glass surface 2 Sample 3 Horizontal surface

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 319/20 C07C 319/20 323/20 323/20 (72) Inventor Yasuhiro Shimizu 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Chemicals Limited

Claims (6)

[Claims] 1. A bromine or bromine solution obtained by dissolving a compound having an aliphatic unsaturated bond represented by the following formula (1) or a solution obtained by dissolving the compound having an aliphatic unsaturated bond in a solvent inert to bromine: To the compound having an aliphatic unsaturated bond, and the compound having an aliphatic unsaturated bond is added to the compound having the following formula (3) per 100 units of the unsaturated group.
A method for producing a bromine compound represented by the following formula (2), wherein a compound having a hydroxyl group represented by the formula is used in an amount corresponding to 0.5 to 10 hydroxyl groups. Embedded image (Where X is a halogen atom, m and n are integers of 1 to 6, Ar ¹ and Ar ² may be the same or different, and may be an aromatic hydrocarbon group having 5 to 16 carbon atoms or 5 to 16 carbon atoms. 12
Represents a saturated alicyclic hydrocarbon group of the formula, Y is a kind selected from 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 and a single bond. R ¹ and R ² are each a hydrocarbon group having 2 to 11 carbon atoms and having at least one aliphatic unsaturated group. ) (Where X, m, n, Ar ¹ , Ar ² and Y are the same as those in the above formula (1), and R ³ and R ⁴ are the respective fats of R ¹ and R ^{2 in} the above formula (1)) At least one of the group unsaturated groups additionally contains bromine.) (In the formula, R ⁵ is an aliphatic group having 1 to 4 carbon atoms and 1 to 6 carbon atoms, and u represents an integer of 1 to 4.) 2. The concentration of water in a solution obtained by dissolving a compound having an aliphatic unsaturated bond in a solvent inert to bromine, bromine or a bromine solution and a reaction solution substantially consisting of a compound having a hydroxyl group, For a compound having an aliphatic unsaturated bond, the number of water molecules is 1 per 100 unsaturated groups.
The method for producing a bromine compound according to claim 1, wherein the amount is equal to or less than 0. 3. The method for producing a bromine compound according to claim 1, wherein the compound having an aliphatic unsaturated bond is a compound represented by the following formula (4). Embedded image (Where m and n are integers of 2 to 4, Ar ¹ and Ar ² may be the same or different, and a phenyl group, a tolyl group,
Represents a xylyl group or a naphthyl group, Y is a kind selected from methylene, isopropylidene, cyclohexylidene, sulfone, sulfide, ketone and a single bond, and R ¹ and R ² each represent at least an aliphatic unsaturated group;
It is a hydrocarbon group having 2 to 11 carbon atoms. ) 4. A compound having an aliphatic unsaturated bond,
2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane, 2,2-bis {(3,5-dibromo-4-isobutenyloxy) phenyl} propane, bis {(3 5-dibromo-4-allyloxy) phenyl {methane, bis {(3,5-dibromo-4-isobutenyloxy) phenyl} methane, (3,3 ′, 5,
5'-tetrabromo-4,4'-diallyloxy) biphenyl, (3,3 ', 5,5'-tetrabromo-4,
4'-divinyloxy) biphenyl, bis {(3,5-
The method for producing a bromine compound according to claim 1, which is one kind of compound selected from dibromo-4-allyloxy) phenyl} sulfone and bis {(3,5-dibromo-4-isobutenyloxy) phenyl} sulfone. 5. The compound having a hydroxyl group is represented by the following formula (5):
The method for producing a bromine compound according to claim 1, which is a compound represented by the formula: Embedded image (Wherein, R ⁵ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms and 1 to 6 carbon atoms or a saturated hydrocarbon group having 1 to 4 carbon atoms and containing oxygen or sulfur, and u is an integer of 1 to 2) Represents.) 6. The compound having a hydroxyl group is methanol,
Ethanol, n-propanol, i-propanol, n
-Butanol, i-butanol, sec-butanol,
The method for producing a bromine compound according to claim 1, which is at least one compound selected from the group consisting of tert-butanol, allyl alcohol, ethylene glycol and diethylene glycol.