JPH1129513A - 2,2-bis(3,5-dibromo-4-(2,3-dibromopropyloxy)phenyl)propane solid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 2, 2-bis[3,5-dibromo-4-(2,3-dibromopropyloxy)phenyl]propane solid excellent in storage stability and flowability. SOLUTION: This 2,2-bis[3,5-dibromo-4-(2,3-dibromopropyloxy)phenyl]propane solid has a characteristic that the inclination angle of a glass surface is 5-7 deg., when the solid begins to slide. The measurement is carried out by putting the solid on the glass surface having an average roughness of 0.01-0.5 μm on the central line, heating the glass surface at 60 deg.C for 3 hr, and subsequently lifting one end of the heated glass surface to incline the glass surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a 2,2- (2,2-)-method having excellent fluidity and good long-term storage stability as a flame retardant for synthetic resins.
Bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane (hereinafter referred to as TBA-BE
Abbreviated as).

[0002]

2. Description of the Related Art TBA-BE has been put to practical use as a flame retardant for synthetic resins, and is known to be extremely useful especially as a flame retardant such as polypropylene resin and polystyrene resin (Japanese Patent Publication No. 50-35103). Gazette, Tokubo Sho5
0-23693).

As a method for producing TBA-BE, 2,2-bis (3,5-dibromo-4-allyloxyphenyl) propane (hereinafter abbreviated as TBA-AE) is converted to bromine in a good solvent such as methylene chloride. A method of solidifying from a reaction solution obtained by the reaction is known.

[0004] However, in general, the purity of TBA-BE obtained by the conventional method is not always high,
Agglomeration easily occurs under high humidity conditions. Due to this property, there is a problem that phenomena such as blocking during long-term storage occur.
When such a phenomenon occurs, it is necessary to take measures such as crushing and crushing before use, which significantly impairs production efficiency. Moreover, the fluidity of the TBA-BE powder itself is not good, and there is a strong demand for improvement of these properties. When such solids are subjected to a dry heat treatment under specific conditions and evaluated for cohesiveness by a gradient method, the inclination angle is significantly increased as compared with the purified solids, and in some cases, no slip occurs. Was also confirmed.

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies with the aim of providing TBA-BE having excellent storage stability and fluidity. The TBA-BE solid having an angle of about 70 ° was found to have good storage stability and fluidity, and reached the present invention.

[0006]

According to the present invention, a solid is placed on a glass surface having a center line average roughness of 0.01 to 0.5 μm, heated at 60 ° C. for 3 hours, and then subjected to a heat treatment. 2,2-bis [3,5-dibromo-4- (2,2) in which the tilt angle of the glass surface when the solid begins to slide is in the range of 5 to 70 ° 3-
Dibromopropyloxy) phenyl] propane solid is provided.

In the present invention, the inclination angle is measured. The measuring method of the inclination angle is as follows.
The TBA-BE solid is placed on a 0.5 μm glass surface and heated at 60 ° C. for 3 hours. Then, the smooth glass surface on which the heat-treated TBA-BE solid was placed,
Place on a horizontal surface. Next, one end of the smooth glass surface on which the TBA-BE solid is placed is lifted and gradually tilted (in this case, the other end is in contact with the horizontal surface). And the TBA on this smooth glass surface
-When the BE solid begins to slide, measure the angle between the horizontal surface as viewed from the side and the smooth glass surface on which the TBA-BE solid is placed.

[0008] The TBA-BE solid in the present invention is a TBA-BE solid having the above inclination angle of 5 to 70 °, preferably 5 to 65 °, more preferably 5 to 60 °. The inclination angle referred to here means a change in the fluidity (degree of aggregation) of the solid due to the heat treatment, and is obtained by measuring using a protractor or the like. If the inclination angle is greater than 70 °, storage stability is poor, and a blocking phenomenon is likely to occur,
Further, the fluidity is low, and handling becomes difficult, which is not preferable.

The glass surface on which the TBA-BE solid used in the above-described method for measuring the tilt angle is placed has a center line average roughness (Ra) of 0.01 to 0.5 μm, preferably 0.0 to 0.5 μm.
Those having a thickness of 2 to 0.3 μm, substantially about 0.1 μm are used. The center line average roughness is measured by a stylus electric center line average roughness measuring instrument. As such a glass surface, borosilicate glass (Pyrex glass manufactured by Iwaki Glass Co., Ltd.) is used.

According to the present invention, the inclination angle of 5 to 70 ° (60 ° C., 3
The method for producing TBA-BE having after heating for a period of time is not particularly limited. For example, a poor solvent such as methanol is added to a solution of TBA-BE dissolved in a good solvent such as methylene chloride while stirring. Is added successively to precipitate, the concentration of TBA-BE in the good solvent is 45 to 55% by weight, the amount of the poor solvent to be used is 0.5 to 10 times the weight ratio to the good solvent, The addition rate was 1 to 6 kg / hour for 1 kg of the good solvent in the TBA-BE solution, and the temperature was 2
The TBA-BE precipitated under the conditions of 0 to 50 ° C is filtered and dried to obtain a target TBA-BE solid. It is conceivable that the TBA-BE solid having low purification purity partially causes a fusion phenomenon even under a temperature condition equal to or lower than the melting point of TBA-BE. A low value of the tilt angle (after heating at 60 ° C. for 3 hours) means that the impurity concentration is lower, and a certain tilt angle disclosed in the TBA-BE solid of the present invention. Square (after heating at 60 ° C for 3 hours)
It is considered that the difference in the absolute value of also means that a change is expressed in the crystal structure aggregate.

The TBA-BE powder obtained according to the present invention has excellent powder properties, especially excellent fluidity. Characteristic values indicating such fluidity include a repose angle and a spatula angle,
The angle of repose is preferably from 10 to 50 °, more preferably from 20 to 45 °. Further, the spatula angle is preferably from 10 to 60 °, more preferably from 20 to 50 °. If the angle of repose exceeds 50 ° or the spatula angle exceeds 60 °, the fluidity becomes low, and handling becomes difficult, which is not preferable.

The TBA-BE powder obtained according to the present invention is extremely useful as a flame retardant such as a polypropylene resin and a polystyrene resin.

[0013]

The present invention will be described in more detail with reference to the following examples. The purity was determined by high performance liquid chromatography, and the tilt angle (after heating at 60 ° C. for 3 hours), the storage stability test, and the fluidity were in accordance with the following evaluation methods (1) to (3).

(1) Inclination angle (after heating for 3 hours at 60 ° C.) A 0.5 g TBA-BE solid 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 heated at 60 ° C. for 3 hours using a hot air circulating drier, then 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 with one end 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.

(2) Storage stability test TBA-BE powder sample 1 was placed in a cylindrical cell having an inner diameter of 20 mmφ.
0 g, and in a hot air circulating drier maintained at 40 ° C., while applying a weight of 0.2 kgf to the powder layer from the top of the cell.
Stored for months. After 3 months, observe the degree of blocking of the powder taken out of the cell. If there is no change in appearance compared to before the test, ◎, although the powder is hardened, it can be easily touched by hand The sample returned to was indicated by ○, and the sample whose powder layer was solidified and did not collapse even when touched by hand was indicated by ×.

(3) Fluidity The angle of repose and the angle of spatula were measured using a powder tester made by Hosokawa Micron. The angle of repose was measured using a funnel on a horizontally placed disk (D; 80 mm) with a TBA-BE.
Powder is supplied and deposited, and the height (Hm
m) was measured, and the angle of repose Φr was determined by the following equation. Φr = tan (2H / D) The spatula angle is such that a metal spatula having a length of 130 mm and a width of 22 mm is inserted into a powder layer contained in a container, and then the container is lowered and the spatula is placed on the metal spatula. The angle of the side surface of the remaining powder layer was determined with a protractor.

Example 1 100 g of commercially available TBA-BE (FG-3100, manufactured by Teijin Chemicals Ltd.) and 100 g of methylene chloride were placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and dissolved at 25 ° C. I let it. Then, the solution was maintained at 25 ° C., and 200 g of methanol was added to 3 g /
Minutes of addition. After completion of the dropwise addition of methanol, stirring was further continued at the same temperature for 30 minutes. TBA-B precipitated
E was taken out by filtration, and dried under reduced pressure at 80 ° C. to obtain 97 g of TBA-BE powder. Table 1 shows the results of the measurement of the powder by the evaluation method described above.

Example 2 100 g of commercially available TBA-AE (manufactured by Teijin Chemicals Ltd., FG-3200) and 170 g of methylene chloride were placed in a flask equipped with a thermometer, a stirrer and a reflux condenser, and dissolved at 20 ° C. I let it. Next, 54 g of bromine was added dropwise to this solution over 1 hour, and stirring was continued at the same temperature for 1 hour.

To this solution was added 30 ml of a 25% aqueous sodium bisulfite solution to remove excess bromine.
After neutralization with 11 ml of 4% aqueous sodium hydroxide solution, 150
After washing with pure water, the methylene chloride solution of TBA-BE was obtained.

The solution was maintained at 25 ° C., and 147 g of methanol was added dropwise at a rate of 4 g / min with stirring. After completion of the dropwise addition of methanol, stirring was further continued at the same temperature for 30 minutes.
The precipitated TBA-BE was filtered out, taken out under reduced pressure at 80 ° C., and dried to obtain 147 g of TBA-BE powder. Table 1 shows the results of the measurement of the powder by the evaluation method described above.

Example 3 100 g of commercially available TBA-AE (manufactured by Teijin Chemicals Ltd., FG-3200) and 170 g of methylene chloride were placed in a flask equipped with a thermometer, a stirrer and a reflux condenser, and dissolved at 20 ° C. I let it. Next, 54 g of bromine was added dropwise to this solution over 1 hour, and stirring was continued at the same temperature for 1 hour. To this solution was added 30 ml of a 25% aqueous sodium bisulfite solution to remove excess bromine, neutralized with 11 ml of a 24% aqueous sodium hydroxide solution, washed with 150 ml of pure water, and washed with a methylene chloride solution of TBA-BE. I got This solution was maintained at 35 ° C., and 147 g of methanol was added dropwise at a rate of 4 g / min with stirring. After completion of the dropwise addition of methanol, stirring was further continued at the same temperature for 30 minutes. The precipitated TBA-BE was filtered out and taken out.
The TBA-BE powder 146
g was obtained. Table 1 shows the results of the measurement of the powder by the evaluation method described above.

Comparative Example 1 100 g of commercially available TBA-AE (manufactured by Teijin Chemicals Ltd., FG-3200) and 170 g of methylene chloride were placed in a flask equipped with a thermometer, stirrer, and reflux condenser, and dissolved at 20 ° C. I let it. Next, 54 g of bromine was added dropwise to this solution over 1 hour, and stirring was continued at the same temperature for 1 hour. To this solution was added 30 ml of a 25% aqueous sodium bisulfite solution to remove excess bromine, neutralized with 11 ml of a 24% aqueous sodium hydroxide solution, washed with 150 ml of pure water, and washed with a methylene chloride solution of TBA-BE. I got The resulting solution was heated to distill off methylene chloride, and when the volume of the solution reached 100 ml, 36 g of methanol was added all at once with stirring to solidify. The obtained solid was taken out, mechanically pulverized, and then dried at 80 ° C. under reduced pressure to obtain 149 g of TBA-BE powder. Table 1 shows the results of the measurement of the powder by the evaluation method described above.

[0023]

[Table 1]

[0024]

The TBA-BE powder having a tilt angle of 5 to 70 ° (after heating at 60 ° C. for 3 hours) obtained by the present invention is excellent in storage stability and fluidity. There is something special.

[Brief description of the drawings]

FIG. 1 is a diagram showing a tilt angle in evaluation of a tilt angle (after heating at 60 ° C. for 3 hours).

[Explanation of symbols]

 1 Glass surface 2 TBA-BE solid sample 3 Horizontal surface

Claims (1)

[Claims] 1. A solid is placed on a glass surface having a center line average roughness of 0.01 to 0.5 μm, heated at 60 ° C. for 3 hours, and then tilted by raising one end of the heat-treated glass surface. When the glass surface starts to slide, the inclination angle of the glass surface is 5-7.
2,2-bis [3,
5-Dibromo-4- (2,3-dibromopropyloxy) phenyl] propane solid.