JPH01306436A - Flame retardant for organic polymer substance - Google Patents

Abstract

PURPOSE:To obtain the subject flame retardant containing a reaction product prepared by reacting a bifunctional epoxy compound with a bromine-substituted phenylphenol and phenolic compound in a specific proportion as an essential component without affecting various characteristics, such as flame retardance, with the kind of an organic polymer substance. CONSTITUTION:The objective flame retardant containing a reaction product obtained by reacting (A) one mol bifunctional epoxy compound (e.g., prepared by reacting a dihydroxy compound, such as bisphenol A, with an epihalohydrin) with (B) 0.8-2.0mol phenolyphenol substituted by 5-9 bromines (e.g., pentabromophenylphenol) and (C) 0-1.2mol phenolic compound as an essential component.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to flame retardants for organic polymeric substances.

[Conventional technology]

(Background) Organic polymeric substances are substances that can provide polymeric materials with various excellent properties, and various resin materials obtained from this substance are used for household and industrial electrical equipment parts, It is used in large quantities in a wide variety of applications, including textile products, daily necessities, interior decorations, screw materials, and structures. However, since many organic polymeric substances are constructed based on carbon-carbon bonds, they are inevitably flammable, and are therefore subject to restrictions in terms of use. Therefore, in order to impart flame retardancy to these polymeric substances, flame retardants are usually added.For this purpose, flame retardants such as halogen-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds, etc. In many cases, it is used in combination with flame retardant aids such as antimony trioxide. (Problems with conventional technology) However, when these conventional flame retardants are used in organic polymer materials. ■ Due to poor compatibility between the flame retardant and the organic polymer material, it is difficult to obtain uniform mixing, and therefore sufficient flame retardancy cannot be obtained. ■ Adversely affects the workability during molding of the organic polymeric material and the mechanical properties of the molded product; ■ Other additives present in the organic polymeric material, such as plasticizers, lubricants, antioxidants, etc. Disadvantages such as interfering with the effects of colorants, stabilizers, ultraviolet absorbers, etc. are often observed. Therefore, recently, brominated epoxy compounds have been developed as new flame retardants that eliminate the drawbacks of the conventional flame retardants. However, even when water flame retardants are applied to organic polymeric substances, depending on the type of organic polymeric substance, there may be problems such as insufficient flame retardancy, poor compatibility and thermal properties, workability of the organic polymeric substance to be blended, and problems with molded products. The occurrence of drawbacks such as deterioration of mechanical properties and deterioration of electrical properties cannot be avoided.

[Problem to be solved by the invention]

Therefore, the problem to be solved by the present invention is that the properties such as flame retardancy, compatibility, heat resistance, workability, mechanical properties of molded products, and gas properties vary depending on the type of organic polymer material. The purpose of the present invention is to provide a flame retardant with unprecedented versatility. (Margin below)

[Means to solve the problem]

(Summary) In order to achieve the above object, the flame retardant according to the present invention contains 5 to 9 aiaia per mole of the trifunctional epoxy compound.
It is characterized by containing as an essential component a reaction product obtained by reacting phenylphenol in a ratio of 0.8 to 2.0 moles and a phenol compound in a ratio of O to 1.2 moles (trifunctional epoxy compound). Examples of the bifunctional compound used in the present invention include compounds obtained by reacting a dihydroxy compound with shrimp halogenhydrin or methyl shrimp halogenhydrin. In addition, "dihydroxy compound°°" herein refers to, for example, bisphenol A, bisphenol sulfone, tetrabromobisphenol A, tetrabromobisphenol sulfone, ethylene glycol, propylene glycol,
Pentyl glycol, dibromopentyl glycol, hydroquinone, bisphenol ethane, tetrabromo bisphenol ethane, etc. In addition, "ebihalogenhydrin" or "methylebihalogenhydrin" means, for example, epichlorohydrin, ebibromohydrin, methylepichlorohydrin, methylebibromohydrin, and the like. (Polybromophenylphenol) Examples of the 5-9 bromine-substituted phenylphenol include pentabromophenylphenol, hexabromophenylphenol, heptabromophenylphenol, octabromophenylphenol, and nonabromophenylphenol. (Phenol compound) Furthermore, the “phenol compound” in the present invention includes:
For example, phenol, cresol, xylenol, tribromophenol, dibromocresol, monobromo-
Secondary butylphenol. Examples include monochlorophenol, pentabromophenol, pentachlorophenol, and the like. (Left below) (Manufacture of the flame retardant of the present invention) The organic polymeric flame retardant of the present invention may include, for example, the trifunctional epoxy compound, the brominated phenylphenol and phenol compound of 5 to 9 (&g), the presence of a melt Alternatively, in the absence of 1 mole of the trifunctional epoxy compound, 0 to 5 to 9 bromine-substituted phenylphenols are added to 1 mole of the trifunctional epoxy compound at 80 to 170°C using a tertiary amine or quaternary ammonium compound as a catalyst. It is obtained by reacting .8 to 2.0 mol and a phenol compound at a molar ratio of 0 to 1.2 mol. In the above reaction, 5 to 9 bromine-substituted phenyl per mol of the trifunctional epoxy compound The amount of phenol is 0.
When the amount is 8 mol or less or the quantitative ratio of the phenol compound is 1.2
If the amount exceeds molar, sufficient heat resistance stability, dimensional stability,
Mechanical properties and flame retardancy cannot be obtained. [Catalyst] Next, examples of tertiary amine compounds used as catalysts include triethylamine, tributylamine, triallylamine, trioctylamine, dimethylbenzylamine,
Examples include trilaurylamine, pyridine, picoline, quinoline, and the like. Examples of the quaternary ammonium compound include tetrabutylammonium bromide, tetraenal ammonium chloride, trimethylbenzylammonium bromide, lauryltrimethylammonium acetate, and tetramethylammonium propionate. The amount of these catalysts to be used is 0.01 to 5% by weight based on the amount of the epoxy compound used, and the use of excessive amounts impairs economic efficiency. [Solvent] Next, the use of a solvent is not essential for the purpose, but if necessary, for example, toluene, xylene, methyl ethyl ketone,
Solvents such as methanol, ethanol, butanol, cyclohexanol are used. [Reaction Temperature] Generally, a suitable reaction temperature is 80 to 170°C. If the temperature is below the lower limit temperature, the reaction I5 takes a long time, and if the temperature exceeds the upper limit temperature, the color of the reaction product tends to be dull. (Target polymeric substances) Seven organic polymeric substances to which the flame retardant represented by the general formula of the present invention can be applied include, for example, polystyrene resin, polyethylene resin, polypropylene resin, ABS resin, acrylic resin, and polyvinyl chloride resin. , polyphenylene oxide resin, polycarbonate resin, polyamide resin, saturated or unsaturated polyester resin, melamine resin, epoxy resin, phenol resin, cellulose material, and the like. (Addition Conditions) The amount of the flame retardant of the present invention added is arbitrary, but preferably 2 to 50% by weight based on the target organic polymer substance. The timing of adding the flame retardant of the present invention is when the organic polymer substance is properly mixed;
It may be applied at any time such as during molding or spinning, or any other time when uniform dispersion within the target organic polymer material can be expected. The flame retardant of the present invention may be added as such, dissolved in a solvent, or in the form of nibbles dispersed in water or oil. (Other additives) The flame retardant of the present invention may contain other flame retardants and flame retardant aids, if necessary.
For example, halogen alkyl phosphor phosphate, halogen-containing alkyl phosphite. It can be used in combination with metal oxides, gold hydroxides, alkyl fully bent compounds, etc., if desired. It is also possible to use other known additives (for example, stabilizers, colorants, weatherability imparting agents, ultraviolet absorbers, matting agents, antistatic agents, extenders, etc.).

[Effect]

The flame retardant of the present invention not only provides excellent flame retardancy to various polymeric materials, but also provides excellent flame retardancy and heat resistance when reusing chipped flame-retardant polymeric materials. It is a versatile flame retardant. (Margin below)

【Example】

Hereinafter, modes and effects of implementing the invention will be exemplarily explained using Examples and Comparative Examples. In addition, in each example, “%
" means "% by weight" and "1 part" means "parts by weight." Production Example 1 In a 3-piece separable flask, 880 g (1 mol) of diglycidyl ether of tetrabromobisphenol A and 1.258 g (1 mol) of hexabromophenylphenol were added.
95 mol) and 300 g of xylene were added and heated to 130°C to dissolve them. Next, 6.8 g of triethylamine was added while stirring the contents, and after reacting at 130 to 140°C for 5 hours, the temperature was increased to 170°C. The temperature was raised to distill off xylene, and the mixture was cooled to 140° C. and the reaction product (target product) was taken out. Target oxirane oxygen 0.08%, acid value 0.04Br
65.0% 10% decomposition temperature was 363°C. Production Examples 2 to 7 and Comparative Example 3 In the same manner as Production Example 1, various invention and control flame retardants were synthesized from various polybromophenylphenols and phenol compounds. The formulation of the raw materials and the properties of the reaction products are summarized in Table 1 below. (Left below) 1゜ High Impact (old) polystyrene resin 100 parts
15 parts of the various flame retardants shown in the table and 5 parts of antimony trioxide were added and kneaded at 200"C for 6 minutes to prepare test pieces, and the flame retardance and weather resistance were measured. The results are shown in Table 2 below. Table 2 Note 1) Performed in accordance with UL94 (1/8”). Usage example 2 100 parts of ABS resin and 1 part of various flame retardants shown in Table 1
5 parts of antimony trioxide and 5 parts of antimony trioxide were added and kneaded at 200° C. for 6 minutes to prepare a test piece, and the flame retardance was measured. The results are shown below as a t53 table. f53 table note 2) Conducted according to UL94 (1/8"). Usage example 3 Add 10 parts of the various flame retardants shown in Table 1 and 5f!1! of antimony trioxide to 100 parts of polyethylene resin, and add 17
Test pieces were prepared by kneading at 0° C. for 6 minutes, and flame retardancy and migration properties were measured. The results are shown in Table 4 below. (Margin below) Table 4 Note 3) Used in accordance with JIS K-7201. Note 4) Test piece 150X 3. OX 50a+m
Calculated using the following formula after being exposed to an atmosphere at a temperature of 70°C for 168 hours. Usage example 4 Add 5 parts of barium metasilicate and 10 parts of various flame retardants to 100 parts of polyethylene terephthalate, and heat at 260°C.
Knead for a minute to create a test piece, test for flame retardancy, migration properties,
Tensile strength and bending strength were measured. The results are shown in the t55 table below. Table 5 Note 5) Ratio; Comparative Example Note 6) Conducted in accordance with UL-94 (+/16''). Note 7) Conducted in accordance with JIS K 6911. Note 8) Conducted in accordance with JIS K 8!311. Hori Δ1 Polyamide resin To 80 parts, 10 parts of polycarbonate, 10 parts of various flame retardants, and 3 parts of antimony trioxide were added, and the mixture was kneaded at 260°C for 6 minutes to prepare test pieces. The results are shown in Table 6 below. (Margin below) Table 6 Usage Example 6 100 parts of unsaturated polyester resin, 12 parts of various flame retardants,
0.5 parts of methyl ethyl ketone peroxide (0.5 parts of dicumyl peroxide and 0.5 parts of cobal naphthenate)
150+am x 100mm
1. Dimensional stability and flame retardancy were determined for the sample obtained by pouring into a mold, vacuum degassing, leaving at room temperature for 0.5 hours, and curing at 40°C for 2 hours and 150°C for 4 hours. evaluated. The results are shown in Table 7 below. Table 7: 200 parts of bisphenol epichlorohydrin resin (1:1 mixture of Epicote Yuki 1001 and 1828) was mixed with 20 parts of various flame retardants, and further m-phenylenediamine 2
After adding 0 parts and mixing thoroughly, 150a+m x 1
00 Ilm mold, and after vacuum degassing, it was left at room temperature for 20 minutes, and then at 40°C for 2 hours. After curing at 150°C for 4 hours, flame retardancy and insulation resistance according to UL-94 were evaluated. The results are shown in Table 8 below. Table 8 Book comparison example

【Effect of the invention】

As explained above, the present invention provides versatility in that properties such as flame retardancy, compatibility, heat resistance, workability, mechanical properties and electrical properties of molded products are not easily affected by the type of organic polymer substance. By being able to provide an excellent flame retardant for the industry, it will be beneficial to the development of organic polymer material application industries and to the improvement of fire safety. Patent applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] 1 A reaction product obtained by reacting 1 mole of a bifunctional epoxy compound with 0.8 to 2.0 moles of 5 to 9 bromine-substituted phenylphenols and 0 to 1.2 moles of a phenol compound. A flame retardant for organic polymer substances, characterized by containing as an essential component.