JP3241528B2 - Tribromophenol granulated product with little caking - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reactive flame retardant for synthetic resins, a flame retardant intermediate or a wood preservative,
The present invention relates to a compression-granulated product of 4,6-tribromophenol by a roller compression method, which has improved sublimability.

[0002]

2. Description of the Related Art Generally, 2,4,6-tribromophenol (hereinafter referred to as TBP) is commercially available as powder having an average particle diameter of about 1 mm or flakes having a side of several mm and a thickness of about 1 mm. However, in these powders or flakes, the TBP itself is sublimable, and whiskers (hair-like crystals) grow during storage, and are entangled with each other, causing significant consolidation.
At the time of preparation, operability becomes extremely poor. For example, a package (paper bag of 20-30 kg, 500-1,000
When taking out from a 0kg-packed flexible container, it is necessary to disintegrate it in the package in advance. However, even when such an operation is performed, a compact of about several 100 mm on one side may remain, so that the fine powder and the compact are mixed, resulting in poor fluidity and uniformity. , Automatic weighing, quantitative supply, etc. are difficult. On the other hand, fine powder has a high adhesiveness, and thus causes clogging and contamination in pipes and containers, causing trouble. Furthermore, TBP has a skin sensitizing property, and when it contacts the skin, it causes inflammation of mucous membranes and eczema-like rash. Therefore, the presence of a large amount of fine powder poses a problem in the working environment. In addition, in the case where the package is charged into a large container and stored for a long period of time in order to streamline the operation, it cannot be taken out of the container due to reconsolidation, so that it is extremely difficult to rationalize the operation. For this reason, TBP powder or flake products have a serious problem in operability, and are not satisfactory as products used in large quantities.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems of TBP, to improve sublimability, and to provide a TBP granulated product having good operability.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have identified a powder or flake product of TBP obtained by compression granulation by a roller compression method. It has been found that the granulated product having a particle size and a surface structure of the present invention hardly sublimates and thus has less caking, is excellent in fluidity, constant capacity and uniformity, and has reduced cohesiveness, adhesion and scattering. Reached.

That is, the present invention is a compression-granulated product of a TBP having a particle size of 3 to 50 mm and a volume-based median pore radius inside the granulated product of 1,000 ° or less by a roller compression method.

Hereinafter, the present invention will be described in detail. The particle size of the TBP granulated product of the present invention is 3 to 50 mm. When the particle size is less than 3 mm, adhesion and scattering become severe, and workability and work environment deteriorate. If the particle size exceeds 50 mm, the consolidation can be suppressed, but the fluidity is deteriorated and the workability is reduced. A more preferred particle size is 3 to 10 mm, and a still more preferred range is 4 to 8 mm. The range of the volume-based median pore radius is 1,000 ° or less, and the preferred range is 50 °.
0 ° or less.

The TBP of the present invention can be synthesized by a general method. For example, it can be synthesized by brominating phenol with bromine in a solvent. Although bromophenol such as 2,4-dibromophenol is contained as an impurity, when TBP is used as a flame retardant, a flame retardant intermediate or a wood preservative, the purity is preferably 95% or more. More preferred purity is 99% or more. T
The BP preferably has a water content of 5% or less. A more preferred range is 1% or less. Regardless of the shape of the powder or flake product, it can be subjected to granulation.

[0008] The TBP granulated product of the present invention can be obtained by a roller compression molding method. This method suppresses the growth of whiskers by applying a pressure of several tens to several thousand kgf / cm ^{2 on} the powder to reduce the surface pore radius. By compression molding, an intermolecular force acts to enable molding. There are two types of roller compression molding methods: a roller compression method using a roll having a horizontal groove, and a roller compression method using a roll having a pocket serving as a matrix around the roller. Granules can be obtained. It is also possible to use a grooveless roll in the roller compaction method.

[0009] The shape of the TBP granulated product of the present invention is not particularly limited, and may be spherical, cubic, columnar, plate-like, granular, or rod-like.

[0010]

The TBP granulated product obtained by the present invention can be used as a reactive flame retardant of synthetic resin, a flame retardant intermediate or a wood preservative. Examples of the reactive flame retardant of a synthetic resin include end-capping of polycarbonate for the purpose of flame retardation, application to an epoxy-modified phenol resin, and the like. As flame retardant intermediates for synthetic resins, terminal blocking of tetrabromobisphenol A type epoxy resin, terminal blocking of tetrabromobisphenol A type polycarbonate, synthetic raw material of polydibromophenylene oxide, bis (2,4,6-tri Used as a raw material for the synthesis of (bromophenyl) ethane.

[0011] The TBP granulated product of the present invention has a smaller pore radius and a dense surface structure as compared with a commercially available powder or flake product, and therefore has less sublimability and can suppress the growth of whiskers. And has characteristics of being excellent in fluidity, constant capacity and uniformity, and having little cohesiveness, adhesion and scattering. As a result, the fluidity is good, and it can be taken out from the package, transferred by a large container such as a tank lorry, supplied in a fixed amount, and stored in a large container, and workability is greatly improved.

[0012]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A row using a roll in which a pocket serving as a matrix was cut around the periphery.
Granulated TBP flakes by the Rahl compression method (manac
TBP-A) was compression-molded using a granulator BSS-601 (manufactured by Shinto Kogyo Co., Ltd.), and crushed to about 5
A compression molded product having a diameter of 4 mm and a thickness of 4 mm was obtained. Roll rotation speed is 3
The processing was carried out under the conditions of 0 rpm, a roll width of 300 mm, and a roll pressure of 80 kg / cm ² (oil pressure) at a throughput of 1,600 kg / hour.
The particle density, particle size and pore distribution of the obtained granulated product were measured by the methods described below. The results are shown in Table 1 and the results of the consolidation test are shown in Table 2. Table 3 shows the observation results.

Particle density: Measured according to JIS K 0061 (Method for measuring density and specific gravity of chemical products) 5.2.2 (Other specific gravity bottle method). The specific gravity bottle used was a Wardon-type specific gravity bottle (JIS R 3503), and the test liquid was pure water. Particle size: The sample was allowed to stand on a horizontal surface in a stable state, and the maximum width in the direction of three axes perpendicular to each other was measured with a caliper.・ Measurement of pore distribution: “Chemical Experiment Course” edited by The Chemical Society of Japan 4
The pore radius distribution was measured by the mercury porosimetry described in the Plate, Vol. 12, p. 486. The measurement was performed using the Autoscan-60 Prosimeter (Q
uanta Chrome Co), measuring range 17 ~ 2,000,
The amount of mercury penetrating into the pores was measured at a pressure of 0.07 to 4,200 kg / cm ² Abs. The following relationship is established between the intrusion pressure P of mercury and the pore radius γ: γ = 2σ cos θ / P (θ and σ are the mercury contact angle,
Surface tension), and the measurement results were evaluated based on the volume-based median pore radius. -Consolidation test: Metal cylinder (diameter 40mm, height 300)
mm), put about 600 g of the sample, and load (1.6 kgf / cm
² ) and a test was conducted at a temperature of 50 ° C. for 45 days. The degree of consolidation was determined by the following equation and evaluated. Degree of consolidation (%) = (consolidated weight) / (total weight) × 100 Observation of sublimation state of surface by microscope: Digestion state of surface was observed by optical microscope. The evaluation was made in the following three stages. ：: No whiskers were observed on the surface. Δ: Whisker is observed. ×: The growth of whiskers is intense.

Example 2 Granulation by Roller Compression Using a Roll with Horizontal Grooves The TBP flake product used in Example 1 was pulverized by a pulverizer, and this was granulated by a granulator IR4 × 10 (manufactured by Hosokawa Micron Corporation). ) And crush it to about 6mm x 3mm
A granulated product having a thickness of 3 mm was obtained. The roll shape is 1, under the conditions of a horizontal groove, a roll rotation speed of 24 rpm, and a roll pressure of 90 kg / cm ² G.
The treatment was performed at a throughput of 000 kg / hour. The particle density, particle size, and pore distribution of the obtained granulated product were measured in the same manner as in Example 1. The results are shown in Table 1, and the results of the consolidation test are shown in Table 2.
Table 3 shows the results of observation of the sublimation state of the surface with a microscope.

Comparative Examples 1 and 2 The TBP used in Example 1 and the particle density, particle size and pore distribution of the TBP pulverized by a pulverizer were measured in the same manner as in Example 1, and the results were tabulated. Table 1 shows the results of the consolidation test, and Table 3 shows the results of observation of the sublimation state of the surface with a microscope.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiko Ohara 92 Minokoki-machi, Fukuyama-shi, Hiroshima Manac Ltd.Minooki Plant (72) Inventor Masao Nakajima 92-Mioki-oki-cho, Fukuyama-shi, Hiroshima Manac Ltd. (56) References JP-A-5-57726 (JP, A) JP-A-54-44625 (JP, A) JP-A-5-194205 (JP, A) Dictionary of organic compounds, 2,4,6-Trib “Lomophenol” (p. 633) (edited by The Society of Synthetic Organic Chemistry, Japan, 1985) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 39/27 A01N 31/08 C09K 21 / 08 A61K 9/16

Claims (1)

(57) [Claims] 1. A compression molding of 2,4,6-tribromophenol having a particle size of 3 to 50 mm and a volume-based median pore radius of 1,000 mm or less inside a granulated product by a roller compression method. Granules.