JPH07291880A - Granulated material of tribromophenol having slight agglomeration - Google Patents

Abstract

PURPOSE:To obtain a compressed granulated material of 2,4,6-tribromophenol useful as a reaction type flame-retardant for a synthetic resin, having specific particle diameters and prescribed median pore radii based on volume, slight aggregation, adhesion, scattering properties and sublimation and excellent fluidity, fixed volume and uniformity. CONSTITUTION:This granulated material of 2,4,6-tribromophenol has 3-50mm particle diameters and <=10,000 median pore radii based on volume. The granulated material is obtained in a spherical, cubic or laminar shape by a compression molding method such as slug tableting method for applying tens to several thousands kgf/cm<2> pressure to powder.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is useful as a reactive flame retardant for synthetic resins, a flame retardant intermediate, or a wood preservative.
The sublimation property of 4,6-tribromophenol compressed granules is improved.

[0002]

2. Description of the Related Art 2,4,6-Tribromophenol (hereinafter referred to as TBP) is generally commercially available as a powder having an average particle size of about 1 mm or a flake product having a side of several mm and a thickness of about 1 mm. However, in these powders or flakes, TBP itself is sublimable, whiskers (hairy crystals) grow during storage, and they become entangled with each other and cause significant solidification, so they are taken out, transferred, and transferred.
The operability will be extremely poor during preparation. For example, a package (20 to 30 kg packed paper bag, 500 to 1,000)
It is necessary to crush it in the package before taking it out from a 0 kg stuffing flexible container). However, even if such an operation is performed, there is a case where a solidified substance with a side of several hundred mm remains, so that fine powder and the solidified substance are mixed, resulting in poor fluidity and uniformity. , It is difficult to do automatic weighing and quantitative supply. On the other hand, since the fine powder has a large adhesiveness, it may cause clogging or contamination in the piping or the container and cause a trouble. Furthermore, TBP has a skin sensitizing property, and when it contacts the skin, it causes inflammation of the mucous membrane and eczema-like rash, so that the presence of a large amount of fine powder poses a problem in the working environment. Further, in order to rationalize the work, if the container is put in a large container and stored for a long period of time, it will be impossible to take out from the container due to re-solidification, which makes it extremely difficult to rationalize the work. Therefore, the TBP powder or flake product has a serious problem in operability and is not satisfactory as a product used in a large amount.

[0003]

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

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a specific particle size obtained by compression granulating TBP powder or flakes It was found that the granulated product having a surface structure is less likely to be sublimated so that it is less likely to be solidified, is excellent in fluidity, constant volume property and uniformity, and is reduced in cohesiveness, adhesiveness and scattering property, and thus reached the present invention.

That is, the present invention has a particle size of 3 to 50 mm and a volume-based median pore radius of 1 inside the granulated product.
It is a TBP compression granulated product with a volume of 10,000 or less.

The present invention will be described in detail below. The particle size of the TBP granulated product of the present invention is 3 to 50 mm. If the particle size is less than 3 mm, the adhesion and scattering will be severe, and the workability and working environment will be poor. When the particle size exceeds 50 mm, the solidification can be suppressed, but the fluidity deteriorates and the workability deteriorates. A more preferable particle size is 3 to 10 mm, and a more preferable range is 4 to 8 mm. The volume-based median pore radius is 10,000 Å or less, and when it exceeds 10,000 Å, sublimation is intense and solidification is large. A preferred volume-based median pore radius range is 1,000 Å or less, and a more preferred range is 500 Å 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. A more preferable purity is 99% or more. T
The water content of BP is preferably 5% or less. A more preferable range is 1% or less. The powder may be in the form of powder or flakes and may be subjected to granulation.

The TBP granulated product of the present invention can be obtained by a compression molding method. This method is used for powders of tens to thousands.
The pressure of kgf / cm ² is applied and the pore radius of the surface is reduced to suppress the growth of whiskers.
By compression molding, intermolecular force works and molding becomes possible. There are three types of compression molding methods: a slug tableting method, a roller compression method using a roll with a horizontal groove, and a roller compression method using a roll with pockets forming a mother die around it. The TBP granulated product of the invention can be obtained.
It is also possible to use rolls without grooves in the roller compaction method.

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

[0010]

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

The TBP granulated product of the present invention has a smaller pore radius and a denser surface structure than commercially available powder or flake products, so that it has less sublimation property and can suppress the growth of whiskers. It is possible to suppress the above, and it is excellent in fluidity, constant capacity, and uniformity, and there is little cohesiveness, adhesiveness, and scattering property. As a result, the fluidity is good, and it is possible to take it out from the package, transfer it in a large container such as a tank truck, supply it in a fixed amount, and store it in a large container, which greatly improves the workability.

[0012]

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 roll using a roll in which a pocket serving as a mother die is cut around the periphery.
Granulated TBP flake product (TBP-A manufactured by Manac) by the Rahr compression method is compression molded using a granulation granulator BSS-601 (manufactured by Shinto Kogyo Co., Ltd.) and crushed to obtain a diameter of about 5 mm x A compression molded product having a thickness of 4 mm was obtained. Roll speed is 30 rpm, roll width is 300
mm, roll pressure 80kg / cm ² (hydraulic pressure), 1,60
It was carried out at a throughput of 0 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, the consolidation test results are shown in Table 2, and the surface sublimation state by a microscope is measured. The observation results are shown in Table 3.

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 in a stable state on a horizontal plane, and the maximum widths in the three axial directions orthogonal to each other were measured with a caliper.・ Measurement of pore distribution: "Experimental Chemistry" edited by Chemical Society of Japan 4
The pore radius distribution was measured by the mercury intrusion method described in pp. 12, 486, ed. Measurement is Autoscan-60 Prosimeter (Q
uanta Chrome Co), measuring range 17-2,000,
The amount of mercury penetrating into the pores was measured at 000Å and a pressure range of 0.07 to 4,200 kg / cm ² Abs. The following relationship holds between the mercury penetration pressure P and the pore radius γ: γ = 2σ cos θ / P (θ and σ are the contact angle of mercury and
The surface tension) and the measurement results were evaluated by the volume-based median pore radius. -Caking test: Metal cylinder (diameter 40 mm, height 300)
mm), put about 600g of sample, and load (1.6kgf / cm
^The test was conducted for 45 days at a temperature of 50 ° C. under the condition ² ). The degree of solidification was calculated by the following formula. Consolidation degree (%) = (consolidation weight) / (total weight) × 100 Observation of surface sublimation state with a microscope: The digestion state of the surface was observed with an optical microscope. The evaluation was made into the following three stages. ◯: Whiskers are not recognized on the surface. Δ: Whiskers are recognized. X: Whiskers are growing rapidly.

Example 2 Granulation by Roller Compression Method Using Roll with Horizontal Grooves The TBP flake product used in Example 1 was pulverized by a pulverizer, and this was granulated by IR4 × 10 (manufactured by Hosokawa Micron Co., Ltd.). ) Compression molding, crushing it and approx. 6 mm x 3 mm
A granulated product with a thickness of 3 mm was obtained. Roll shape is horizontal groove, roll speed 24rpm, roll pressure 90kg / cm ² G
The throughput was 000 kg / hour. The particle density, particle size and pore distribution of the obtained granulated product were measured by the same method as in Example 1, the results are shown in Table 1, the consolidation test results are shown in Table 2,
Table 3 shows the results of observation of the sublimated state of the surface with a microscope.

Example 3 Granulation by slug tableting method The TBP flake product used in Example 1 was converted into a tablet machine HT-
Approximately 1 by tableting with E5-S (manufactured by Tamagawa Machinery Co., Ltd.)
Two types of compression molded products having a diameter of 5 mm × 15 mm and a diameter of about 20 mm × 9 mm were obtained. The punch set was two sets of φ flat, and the rotation speed was 10 rpm. The particle density, particle size and pore distribution of the obtained granulated product were measured by the same method as in Example 1, the results are shown in Table 1, the consolidation test results are shown in Table 2,
Table 3 shows the results of observation of the sublimated state of the surface with a microscope.

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

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Ohara 92 Minooki-cho, Fukuyama-shi, Hiroshima Manac Co., Ltd.Minooki Plant (72) Inventor Masao Nakajima 92 Mino-oki, Fukuyama-shi, Hiroshima Manac Co., Ltd.

Claims (1)

[Claims] 1. The particle size is 3 to 50 mm, and the volume-based median pore radius inside the granulated product is 10,000 Å or less 2.
4,6-tribromophenol compressed granulation product.