JPH0133092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel compound brominated phenol derivatives for use as flame retardants. Among polymeric materials, raw material polymers, such as various thermoplastic resins and thermosetting resins, are generally easily combustible, and as demands for their safety have increased, flame retardancy has also been required. In order to make a raw polymer flame retardant, a method is usually adopted in which a halogen-containing and/or phosphorus-containing compound is added and mixed therein as a flame retardant. In this case, the flame retardant used is limited to the type of material polymer. For example, 2.2-bis(4-allyloxy-3.5-dibromophenyl)propane is mainly a styrene resin, and 2.2-bis(4-dibromopropyl-3.5-dibromophenyl)propane is mainly a polyolefin resin. Even if these are used with other polymer materials, excellent flame retardancy cannot be obtained. Recently, polymer blending methods have been adopted for the purpose of modifying raw material polymers, and blended polymers that are blends of raw material polymers have come into existence. In the polymer blend method, there are a wide variety of raw material polymers used, so there is a similarly wide variety of blend polymers. Therefore, with conventional flame retardants limited to the type of material polymer,
It is difficult to make blended polymers flame retardant. Therefore, there is a need for a new compound that can be used as a versatile flame retardant that imparts excellent flame retardancy to a wide variety of raw material polymers and blend polymers. In view of the current situation, the inventors of the present invention have conducted extensive research, and as a result have come to provide the present invention. That is, it is a bromine-containing phenol derivative represented by the following general formula (). A-O-R...() A is

【formula】

[expression] or

[Formula] is shown, and R is

[expression] or

[Formula] is shown. However, A

In [formula], And R is

Exclude combinations that are [expression]. Specific examples of the bromine-containing phenol derivative represented by the general formula () are shown in Table 1.

【table】

[Table] The bromine-containing phenol derivative represented by the general formula () can be prepared by following general synthesis methods described in literature, such as halogenation, dehalogenation, and chloromethylation (Unit Process Series 3; Kagaku Kogyo Co., Ltd.). b) Tribromophenyl dibromopropyl ether, tribromophenyl dibromoisobutyl ether, 2.2-bis(4-dibromoisobutyl-3.5-dibromophenyl)propane, 2.2-bis(4-dibromopropyl-3.5-dibromophenyl) A compound selected from sulfone or 2.2-bis(4-dibromoisobutyl-3.5-dibromophenyl)sulfone and (b) caustic alkali are reacted in water and/or an organic solvent to remove the
Obtained by HBr conversion. Examples of the caustic alkali include caustic soda and caustic potash. Examples of the organic solvent include methanol, isopropyl alcohol, isobutyl alcohol, methylene chloride, dichloropropane, carbon tetrachloride, perchloroethylene, benzene, toluene, and the like. When the bromine-containing phenol derivative represented by the general formula () is used as a flame retardant, it can be applied to polymeric materials such as polystyrene resin, polyethylene resin, polypropylene resin, ABS resin, acrylic resin, etc., but is not particularly limited. based resin,
Vinyl chloride resin, polyphenylene oxide resin,
Material polymers such as polycarbonate resins, polyamide resins, saturated or unsaturated polyester resins, melanin resins, epoxy resins, and phenolic resins, and blend polymers thereof are included. The amount added to the polymeric material is arbitrary, but preferably 0.2 to 30% by weight, and the addition method is in the form of granulation or dissolution in a solvent, or in water or oil. Examples include a method in which it is added in the form of an emulsion in which it is dispersed in a polymeric material during the production of a polymeric material (during polymerization, molding, spinning, etc.) or at other times when it is uniformly mixed. In addition, other known flame retardants and flame retardant aids (for example, halogen-containing alkyl phosphates, halogen-containing alkyl phosphites, metal oxides, metal hydroxides, alkyl metal compounds, etc.) can be used in combination as necessary. It is also possible to use other known additives (for example, stabilizers, colorants, weather resistance agents, solar radiation absorbers, matting agents, antistatic agents, extenders, etc.). The flame retardant of the present invention, which has a brominated phenol derivative represented by the general formula ( It is a versatile flame retardant that provides excellent flame retardancy and heat resistance even when reusing materials. Next, a manufacturing example of the present invention will be shown. Production Example 1 53.1 g of tribromophenyl dibromopropyl ether was placed in a four-necked flask equipped with a reflux condenser.
(0.1 mol), 100 g of isobutyl alcohol, 100 g of dichloropropane, and 10 g (0.12 mol) of a 48% aqueous solution of caustic soda as a caustic alkali were charged, the temperature was gradually raised while heating, and the mixture was stirred at 90° C. for 3 hours. After washing with water and drying, 44.5 g of a crude product was obtained. Next, it was recrystallized twice using a mixed solvent of methanol/acetone=1/1 to obtain 32 g of the bromine-containing phenol derivative No. 1 in Table 1. Production Example 2 54.5 g of tribromophenyl dibromoisobutyl ether instead of 53.1 g (0.1 mol) of tribromophenyl dibromopropyl ether in Production Example 1
(0.1 mol), otherwise the same procedure as in Production Example 1 was carried out, and 37 g of the bromine-containing phenol derivative No. 2 of Table 1 was used.
I got it. Production Example 3 Using 48.6 g (0.05 mol) of 2.2-bis(4-dibromoisobutyl-3.5-dibromophenyl)propane instead of 53.1 g (0.1 mol) of tribromophenyl dibromopropyl ether in Production Example 1,
The rest was carried out in the same manner as in Production Example 1 to obtain 45.7 g of the bromine-containing phenol derivative No. 3 in Table 1. Production Example 4 Instead of 53.1 g (0.1 mol) of tribromophenyl dibromopropyl ether in Production Example 1, 48.3 g (0.05 mol) of 2.2-bis(4-dibromopropyl-3.5-dibromophenyl) sulfone and 100 g of dichloropropane were used. Instead, perchlorethylene 100
The same procedure as in Production Example 1 was carried out except that 44 g of the bromine-containing phenol derivative No. 4 in Table 1 was obtained. Production Example 5 2.2-bis(4-dibromoisobutyl-3.5-dibromophenyl)sulfone 49.7g (0.05mol) and 100g of dichloropropane instead of 53.1g (0.1mol) of tribromophenyl dipromopropyl ether in Production Example 1 perchlorethylene 100 instead of
The same procedure as in Production Example 1 was carried out except that 45.2 g of the bromine-containing phenol derivative No. 5 in Table 1 was obtained. Usage Example 1 2 parts of a bromine-containing phenol derivative represented by the general formula () were added to 100 parts of polystyrene resin, and kneaded for 5 minutes at 190 to 200°C using a hot roll. Next, press at 190-200°C and 150 atm for 3 minutes, then apply to a screw press for cooling. Flame retardancy (ASTM-D2863) and heat resistance (reduction in relative viscosity) of molded products taken out from cooling screw press
and colorability (judgment with the naked eye) was evaluated. Next, the above-mentioned molded product was roughly molded, and the regenerated molded product obtained by kneading and molding was similarly evaluated for flame retardancy, heat resistance, and colorability. The results are shown in Table 2.

【table】

[Table] Usage example 2 50 parts of polypropylene resin, 50 parts of HI-polystyrene resin, 15 parts of a bromine-containing phenol derivative represented by the general formula (), and 5 parts of Sb ₂ O ₃ were kneaded at 180°C for 5 minutes using a hot roll. did. Next, press at 180°C and 150 atm for 3 minutes, then apply to a screw press for cooling. The flame retardance (UL-94) and bleedability of the molded product taken out from the cooling screw press were evaluated. The results are shown in Table 3.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A bromine-containing phenol derivative represented by the following general formula (). A-O-R...() [A represents [Formula] [Formula] or [Formula], R represents [Formula] or [Formula]. However, combinations where A is [formula] and R is [formula] are excluded. ]