JP3796762B2 - Large particle size 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane and method for producing the same - Google Patents

Description

【００４１】
【表２】

実施例２
合成例１で得たＴＢＡ−ＢＰの良溶媒溶液を、表１の条件下、処理し大粒子系ＴＢＡ−ＢＰを得た。得られた大粒子径ＴＢＡ−ＢＰを顕微鏡観察した結果では、粒子径１〜３ｍｍで不定形の一次粒子であることが観察された。結果を表２にあわせて示す。
【００４２】
実施例３
合成例１で得たＴＢＡ−ＢＰの良溶媒溶液を、表１の条件下、処理し大粒子系ＴＢＡ−ＢＰを得た。得られた大粒子径ＴＢＡ−ＢＰを顕微鏡観察した結果では、粒子径１〜２ｍｍで不定形の一次粒子であることが観察された。結果を表２にあわせて示す。
【００４３】
実施例４
調製例１で得たＴＢＡ−ＢＰの良溶媒溶液を、表１の条件下、処理し大粒子系ＴＢＡ−ＢＰを得た。得られた大粒子径ＴＢＡ−ＢＰを顕微鏡観察した結果では、粒子径５〜６ｍｍで不定形の一次粒子であることが観察された。結果を表２にあわせて示す。
【００４４】
実施例５
合成例１又は調製例１で得たＴＢＡ−ＢＰの良溶媒溶液を、表１の条件下、処理し大粒子系ＴＢＡ−ＢＰを得た。得られた大粒子径ＴＢＡ−ＢＰを顕微鏡観察した結果では、粒子径１〜３ｍｍで不定形の一次粒子であることが観察された。結果を表２にあわせて示す。
【００４５】
比較例１
合成例１で得たＴＢＡ−ＢＰ１００ｇを含有するジクロロメタン溶液１００ｇを、撹拌機を備えた１ｌのビーカーに入れたメタノール１２０ｇ中に室温で１時間かけて添加し、ＴＢＡ−ＢＰの製造を試みたところ、メタノール中に分散せず、壁面及び底部にブロック状の固まりとして付着した。
【００４６】
比較例２
シャフト径２ｃｍのホモジナイザーを備えた１ｌのビーカーに、メタノール１００ｇを仕込み室温で撹拌しながら、これに合成例１で得たＴＢＡ−ＢＰ１００ｇを含むジクロロメタン溶液２００ｇを３０分かけて添加し、添加後さらに１時間撹拌し晶析させた。次いで得られたスラリーを濾過、８０℃で減圧乾燥し、ＴＢＡ−ＢＰの粉末９５ｇ、収率９５％で得た。
【００４７】
高速液体クロマトグラフによる純度分析結果は９５．２％、粒子径は１００〜３００μｍ、パウダーテスターによる粉体物性測定結果は安息角５４゜、スパチュラー角７５゜及び崩壊角５２゜で粉体物性は悪かった。また耐熱着色性試験においては、ＡＰＨＡ１５０と悪かった。条件を表１、結果を表２にあわせて示す。
【００４８】
比較例３
撹拌機を備えた１ｌのビーカーにメタノール１００ｇ及び種結晶として実施例１で得られた大粒子径ＴＢＡ−ＢＰ３ｇを入れ、これに合成例１で得たＴＢＡ−ＢＰのジクロロメタン溶液を、室温で１時間かけて添加、さらに同温度で１時間撹拌を行った。
【００４９】
得られた実施例１と同様に濾過、乾燥したところ市販品と比べて比較的粒子径の大きいのＴＢＡ−ＢＰが得られたものの、収率が９２％と低くまた、ビーカーに一部スケーリングが発生していた。条件を表１、結果を表２にあわせて示す。
【００５０】
比較例４
実施例１と同じ装置で、貧溶媒をメタノールからイソプロパノールに替えた以外、実施例１と同様に表１中に示した条件下実施した。ＴＢＡ−ＢＰのジクロロメタン溶液添加中撹拌が困難となり、添加終了時には全く撹拌できない状況であった。条件を表１、結果を表２に示す。
【００５１】
参考例 保存安定性試験
実施例１、実施例４及び比較例２で製造したＴＢＡ−ＢＰを内径２ｃｍの円筒型のステンレス容器に各試料を高さ５ｃｍになるように充填し、熱風循環式の加熱オーブン中で、９０℃で１０時間処理した。処理後、冷却し観察したところ、実施例１及び４の試料については固化等の形状変化はなく粉体であったが比較例２の試料は固化していた。
【００５２】
【発明の効果】
本発明により、耐熱着色性及び粉体物性が良好で樹脂配合時の操作性が改善され、さらに長期保存安定性が改良された、平均粒子径が１ｍｍよりも大きい大粒子径ＴＢＡ−ＢＰが提供される。また本発明の方法は、工業的規模においても、汎用の装置で高収率で経済的に大粒子径ＴＢＡ−ＢＰを製造することができるので、工業的に非常に有用である。
【図面の簡単な説明】
【図１】実施例１にて得られた大粒子径ＴＢＡ−ＢＰの光学顕微鏡による粒子構造を示す写真である。[0001]
[Industrial application fields]
The present invention is a flame retardant for synthetic resin having a large particle size of 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane (hereinafter abbreviated as TBA-BP) having good heat resistance and powder properties. It relates to the manufacturing method.
[0002]
[Prior art]
Conventionally, TBA-BP is a reaction solution obtained by reacting 2,2-bis (3,5-dibromo-4-allyloxyphenyl) propane (hereinafter abbreviated as TBA-BA) with bromine in a good solvent. Methods of adding and crystallizing in a poor solvent are known. TBA-BP is obtained as amorphous fine particles, and commercially available products usually have an average particle size of about 200 μm.
[0003]
For example, in Japanese Patent Application Laid-Open No. 55-111429, a solution of TBA-BP obtained by the reaction of TBA-BA and bromine in a chlorobenzene solvent is added and crystallized in methanol in the presence of seed crystals, and is about 500 to 1000 μm. It is obtained as a granular crystal.
[0004]
In JP-A-57-289, a TBA-BP solution is added to a poor solvent and crystallized by stirring with shearing force to obtain a yellowish white powder.
[0005]
Furthermore, for the purpose of improving the operability and recovery rate, after adding a poor solvent having a boiling point higher than that of the good solvent used in the TBA-BP solution, the good solvent is distilled off by heating and crystallized to obtain white fine powder crystals. Method (JP-A-4-234337), a method in which a solution of TBA-BP is added to heated hot water in the presence of a surfactant and at the same time the good solvent is distilled off and crystallized to obtain a white powder (special Kaihei 4-270236) is known.
[0006]
[Problems to be solved by the invention]
However, the TBA-BP obtained by these conventional methods has a particle size of 1 mm or less, and there are problems of operability such as bridging to the charging hopper when the resin is compounded and blocking occurs during long-term storage. Therefore, treatment such as crushing and crushing was necessary before use. Moreover, the heat resistant colorability was poor in quality, and there was a problem of coloring the resin when the resin was blended.
[0007]
For example, in Japanese Patent Application Laid-Open No. 55-111429, TBA-BP having a particle size of about 500 to 1000 μm can be obtained, but there is a problem that the yield is as low as 94.5%.
[0008]
In JP-A-57-289, TBA-BP having a large particle size cannot be obtained, and a stirrer having a shearing force is required. On an industrial scale, a special stirrer such as a homogenizer is required. there were.
[0009]
Further, in JP-A-4-234337 and JP-A-4-270236, which improve the above problems, it is not possible to obtain TBA-BP having a large particle size, and it is possible to carry out without problems on a small scale. Application on a general scale may cause problems such as scaling during crystallization, and is not an industrial production method.
[0010]
The present invention has been made in view of the above-mentioned problems, and its object is to provide a large particle diameter TBA-BP having an average particle diameter larger than 1 mm, which has good heat-resistant colorability and improved powder physical properties, and a method for producing the same. Is to provide.
[0011]
[Means for Solving the Problems]
The inventors of the present invention have conducted extensive studies on a large particle diameter TBA-BP having an excellent heat resistant colorability and improved powder physical properties, an average particle diameter larger than 1 mm, and a method for producing the same, and as a result of bromination of TBA-BA. The resulting good solvent solution of TBA-BP or a solution obtained by re-dissolving the conventional TBA-BP in a good solvent is added to heated methanol in the presence of seed crystals, and the good solvent is distilled off for crystallization. The TBA-BP having an average particle size larger than 1 mm and a uniform large particle size can be obtained in a high yield, and the powder physical properties and storage stability of the obtained TBA-BP are also found to be good. The present invention has been completed.
[0012]
That is, the present invention relates to a large particle size 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane having a mean particle size larger than 1 mm and a method for producing the same.
[0013]
Hereinafter, the present invention will be described in detail.
[0014]
The large particle diameter TBA-BP of the present invention is an irregular bulk primary particle and has an average particle diameter of more than 1 mm. As the powder physical properties, the angle of repose, which is an index for the ease of handling the powder, is preferably 45 ° or less, more preferably 35 ° or less. In addition, the heat-resistant coloring property is markedly improved as compared with conventional commercial products.
[0015]
The production method of the large particle size TBA-BP of the present invention is not particularly limited, but a solution of TBA-BP dissolved in a good solvent is added dropwise to methanol that has been previously added with seed crystals and heated, and at the same time as the dropping, the good solvent A method of precipitating while distilling out of the system is preferred.
[0016]
Although the good solvent solution of TBA-BP used for this invention is not specifically limited, For example, the reaction liquid obtained by reaction of TBA-BA and a bromine is used. In addition, powder TBA-BP produced by a conventional method may be used again by dissolving it in a good solvent.
[0017]
The particle diameter of the seed crystal used in the present invention is not particularly limited, but may be a commercially available one of about 200 μm, fine particles, or an average particle diameter larger than 1 mm of the present invention. A large particle size TBA-BP may be used, and all of these are applicable.
[0018]
The purity of the seed crystal used in the present invention is not particularly limited, but it is preferably 90% by weight or more.
[0019]
The amount of seed crystals used is usually 0.5% by weight or more with respect to the weight of TBA-BP included in the crystallization, but excessive addition is not economical and preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight.
[0020]
Any good solvent can be used as long as it dissolves TBA-BP and has a lower boiling point (64.7 ° C. or lower) than methanol used as a poor solvent. Isopropyl chloride, n-propyl chloride, tert-butyl chloride, 1,1,1-difluoro-chloroethane, dichloromethane, chloroform, ethyl bromide and other organic halogen compounds, methyl formate, ethyl formate, methyl acetate, β-pro Examples include ester compounds such as piolactone, ether compounds such as diethyl ether, tert-butyl methyl ether and furan, and ketone compounds such as acetone. However, in terms of economy and solubility, organic halogen compounds and diethyl ether. Acetone is preferred and industrially practiced Expediently, dichloromethane, chloroform, acetone more preferred.
[0021]
The TBA-BP concentration in the good solvent can be applied as long as it is below the saturation solubility of TBA-BP in the good solvent to be used. However, if the concentration is too low, the amount of the good solvent to be used becomes enormous and economical. Preferably, it is 5% by weight or more and not more than the saturation solubility in the good solvent.
[0022]
If the amount of methanol used is too small, the slurry concentration of TBA-BP after crystallization becomes high and stirring may become impossible, and use of a large excess is not economical, so it is preferable to use TBA-BP. On the other hand, it is in the range of 0.6 to 10 times by weight, more preferably in the range of 0.8 to 5 times by weight.
[0023]
As for the temperature at the time of crystallization, for a good solvent that does not azeotrope with methanol, the temperature is lower than the boiling point of methanol and higher than the boiling point of the good solvent to be used. The good solvent azeotroped with methanol is carried out at a temperature not higher than the boiling point of methanol and not lower than the azeotropic temperature of the good solvent used with methanol. Furthermore, in order to efficiently distill off the good solvent, it is preferable to carry out at a temperature 5 to 10 ° C. higher than the boiling point of the good solvent used or the azeotropic point of the good solvent and methanol.
[0024]
The crystallization time is limited by the time during which the amount of heat necessary to distill off the good solvent at the same time as the dropwise addition of the good solvent solution of TBA-BP can be supplied, or the ability of the condenser to recover the good solvent to be distilled off. There is no particular limitation.
[0025]
The method and apparatus for recovering the good solvent to be distilled are not particularly limited, and there is no problem with the recovery by simple distillation, but in order to recover the good solvent with high purity, a packed column of 1 to 10 stages is used. Precision distillation may be performed.
[0026]
After adding the good solvent solution of TBA-BP, it may be cooled immediately, or the good solvent remaining in the system may be further distilled off for 1 to 2 hours.
[0027]
After adding the good solvent solution of TBA-BP or further distilling off the good solvent remaining in the system, cooling, filtering, and drying are performed to obtain the desired large particle size TBA-BP.
[0028]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
[0029]
Synthesis Example 1 Synthesis of TBA-BP TBA-BA (500 g) and dichloromethane (720 g) were charged into a 2 liter round bottom three-necked round bottom flask equipped with a stirrer, a thermometer and a Dimroth condenser, and adjusted to 20 ° C. on a water bath. Bromine 283 g was added dropwise over 1 hour, and further aging was performed at the same temperature for 2 hours.
[0030]
Next, 59 ml of an aqueous solution containing 25 g of sodium hydrogen sulfite was added to remove excess bromine, and then washed once with 350 ml of water to obtain a dichloromethane solution of TBA-BP.
[0031]
As a result of analysis by a high performance liquid chromatograph and a gas chromatograph, 718 g of TBA-BP and 715 g of dichloromethane were contained in the solution.
[0032]
Preparation Example 1
A 5-liter beaker was charged with 200 g of commercially available TBA-BP (purity 96.0%) powder and 1700 g of acetone, stirred for 4 hours with a magnetic stirrer and dissolved, and then suction filtered with Nutsé to remove undissolved and insoluble components. The thing was removed and the solution of TBA-BP was obtained.
[0033]
As a result of analyzing the obtained solution with a high performance liquid chromatograph and a gas chromatograph, it contained 172 g of TBA-BP and 1680 g of acetone.
[0034]
Preparation Example 2
In the same manner as in Preparation Example 1, a TBA-BP solution was prepared using 300 g of commercially available powder of TBA-BP (purity 96.0%) and 600 g of chloroform. The obtained solution was similarly analyzed, and as a result, 290 g of TBA-BP and 586 g of chloroform were contained.
[0035]
Example 1
200 g of methanol and 3 g of commercially available TBA-BP (purity 96%, particle size 150 μm) as a seed crystal were added to a 1 liter round bottom separable flask equipped with a stirrer and a distillation condenser, and the mixture was stirred on a hot water bath. To 50 ° C.
[0036]
To this, 200 g of a dichloromethane solution containing 100 g of TBA-BP obtained in Synthesis Example 1 was added dropwise over 2 hours to crystallize TBA-BP. According to the addition of the solution, dichloromethane was distilled out of the system, and maintained at the same temperature for 15 minutes after the addition was completed. The total amount of the distillate was 94 g, and it was composed of 71 g of dichloromethane and 23 g of methanol in the gas chromatographic analysis.
[0037]
Next, the mixture was cooled to room temperature, filtered, and dried under reduced pressure at 80 ° C. to obtain 96.7 g of TBA-BP having a large particle size and a recovery rate of 99.8%. The analysis by high performance liquid chromatograph showed a purity of 97.2%.
[0038]
As a result of observing the obtained large particle diameter TBA-BP under a microscope, it was observed that the particle diameter was 1 to 3 mm and the particles were amorphous primary particles. The particle structure of the obtained large particle diameter TBA-BP is shown in FIG. 1 (× 40).
[0039]
The powder physical properties were measured with a Hosokawa Micron powder tester. As a result, the powder physical properties were very good with an angle of repose of 30 °, a spatula angle of 32 °, and a collapse angle of 20 °. Regarding heat resistance coloring property, 5 g of the obtained TBA-BP having a large particle diameter was put into a test tube, heated in an oil bath at 180 ° C. for 20 minutes under air release, cooled, then dissolved in 100 ml of chloroform, and APHA. Was 40. The conditions are shown in Table 1, and the results are shown in Table 2.
[0040]
[Table 1]

[0041]
[Table 2]

Example 2
The good solvent solution of TBA-BP obtained in Synthesis Example 1 was treated under the conditions shown in Table 1 to obtain a large particle TBA-BP. As a result of observing the obtained large particle diameter TBA-BP under a microscope, it was observed that the particle diameter was 1 to 3 mm and the particles were amorphous primary particles. The results are shown in Table 2.
[0042]
Example 3
The good solvent solution of TBA-BP obtained in Synthesis Example 1 was treated under the conditions shown in Table 1 to obtain a large particle TBA-BP. As a result of observing the obtained large particle diameter TBA-BP with a microscope, it was observed that the particle diameter was 1 to 2 mm and the particles were indefinite primary particles. The results are shown in Table 2.
[0043]
Example 4
The good solvent solution of TBA-BP obtained in Preparation Example 1 was treated under the conditions shown in Table 1 to obtain a large particle TBA-BP. As a result of observing the obtained large particle diameter TBA-BP under a microscope, it was observed that the particle diameter was 5 to 6 mm and the particles were indefinite primary particles. The results are shown in Table 2.
[0044]
Example 5
The good solvent solution of TBA-BP obtained in Synthesis Example 1 or Preparation Example 1 was treated under the conditions shown in Table 1 to obtain a large particle system TBA-BP. As a result of observing the obtained large particle diameter TBA-BP under a microscope, it was observed that the particle diameter was 1 to 3 mm and the particles were amorphous primary particles. The results are shown in Table 2.
[0045]
Comparative Example 1
An attempt was made to produce TBA-BP by adding 100 g of dichloromethane solution containing 100 g of TBA-BP obtained in Synthesis Example 1 to 120 g of methanol in a 1 liter beaker equipped with a stirrer at room temperature over 1 hour. It did not disperse in methanol, but adhered to the wall surface and bottom as a block-like lump.
[0046]
Comparative Example 2
To a 1 liter beaker equipped with a homogenizer having a shaft diameter of 2 cm, 100 g of methanol was charged and stirred at room temperature, and then 200 g of a dichloromethane solution containing 100 g of TBA-BP obtained in Synthesis Example 1 was added thereto over 30 minutes. The mixture was stirred for 1 hour for crystallization. Next, the obtained slurry was filtered and dried under reduced pressure at 80 ° C. to obtain 95 g of TBA-BP powder in a yield of 95%.
[0047]
Purity analysis result by high performance liquid chromatograph is 95.2%, particle size is 100-300μm, powder physical property measurement result by powder tester is repose angle 54 °, spatula angle 75 ° and collapse angle 52 °, and powder property is bad. It was. Moreover, in the heat-resistant coloring property test, it was bad with APHA150. The conditions are shown in Table 1, and the results are shown in Table 2.
[0048]
Comparative Example 3
In a 1 l beaker equipped with a stirrer, 100 g of methanol and 3 g of the large particle size TBA-BP obtained in Example 1 as seed crystals were placed, and a dichloromethane solution of TBA-BP obtained in Synthesis Example 1 was added at room temperature to 1 g. The mixture was added over time and further stirred at the same temperature for 1 hour.
[0049]
When filtered and dried in the same manner as in Example 1, a TBA-BP having a relatively large particle size was obtained as compared with a commercially available product, but the yield was as low as 92% and the beaker was partially scaled. It has occurred. The conditions are shown in Table 1, and the results are shown in Table 2.
[0050]
Comparative Example 4
The same apparatus as in Example 1 was used in the same manner as in Example 1 except that the poor solvent was changed from methanol to isopropanol. Stirring became difficult during the addition of TBA-BP in dichloromethane, and stirring was impossible at the end of the addition. The conditions are shown in Table 1, and the results are shown in Table 2.
[0051]
Reference Example Storage Stability Test TBA-BP produced in Example 1, Example 4 and Comparative Example 2 was filled in a cylindrical stainless steel container having an inner diameter of 2 cm so that each sample had a height of 5 cm, and a hot air circulation type Treated in a heating oven at 90 ° C. for 10 hours. When the sample was cooled and observed after the treatment, the samples of Examples 1 and 4 were in a powder form without any change in shape such as solidification, but the sample of Comparative Example 2 was solidified.
[0052]
【The invention's effect】
According to the present invention, a large particle size TBA-BP having an average particle size larger than 1 mm and improved long-term storage stability with good heat-resistant coloring and powder properties, improved operability at the time of compounding a resin is provided. Is done. In addition, the method of the present invention is very useful industrially because a large particle size TBA-BP can be produced economically in a high yield with a general-purpose apparatus even on an industrial scale.
[Brief description of the drawings]
FIG. 1 is a photograph showing a particle structure of a large particle size TBA-BP obtained in Example 1 using an optical microscope.

Claims (3)

Large particle size 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane , which is a massive primary particle having an average particle size larger than 1 mm and an angle of repose of 35 ° or less .   2. The large particle size 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane according to claim 1, wherein the average particle size is 1.5 to 5.5 mm.   A good solvent solution of 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane obtained by reacting 2,2-bis (3,5-dibromo-4-allyloxyphenyl) propane with bromine, Alternatively, a solution in which 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane is dissolved in a good solvent is added to heated methanol in the presence of seed crystals, and at the same time, the good solvent is distilled off. 3. The method for producing a large particle size 2,2-bis (3,5-dibromo-4-dibromopropoxyphenyl) propane according to claim 1 or 2, wherein crystallization is performed.

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