JPH02129137A - Halogenated bis(4-phenoxyphenyl)ether and flame retardant polymer composition containing the same - Google Patents

Abstract

NEW MATERIAL:A halogenated bis(4-phenoxyphenyl) ether expressed by the formula (X is halogen; a and d are 1-5: b and c are 1-4). EXAMPLE:Octadecabromobis(4-phenoxyphenyl) ether. USE:A flame retardant of polymer material having excellent heat resistancs and migration resistance. PREPARATION:Bis(4-phenoxyphenyl) ether is brominated in the presence of a proper catalyst by a halogenating reagent such as bromine, hydrogen bromide, chloride or chlorinating agent to provide the halogenated bis(4-phenoxyphenyl) ether expressed by the formula. Halogenation degree can be controlled by amount of halogenation reagent and kind of Lewis acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel halogenated bis(4-phenoxyphenyl) ether and a flame-retardant polymer composition containing the same. ] (In formula [I], X represents a halogen atom, a and d are numbers from 1 to 5, and b and c are numbers from 1 to 4). (hereinafter abbreviated as HPPE) and flame-retardant polymer compositions containing the same.

The compound HPPE of the present invention is a compound useful as a flame retardant for polymeric materials.

[Prior Art] Today, various flame retardants are mixed into flammable resins such as polyethylene, polypropylene, and polystyrene for the purpose of making these resins flame retardant.

As flame retardants, various halogen-containing flame retardants, phosphorus-containing flame retardants, phosphorus-containing halogen-containing flame retardants, and inorganic compounds are known.

However, in general, many of these flame retardants have shortcomings in heat resistance, and the flame retardants can cause corrosion of molding machines due to thermal decomposition during polymer molding.

In addition, these flame retardants have poor compatibility with resins and are often low molecular weight, so they may bloom on the resin surface during long-term use in resin compositions or volatilize at high temperatures. It tends to cause changes in the flame retardant properties of the resin.

[Problems to be Solved by the Invention] In recent years, as highly heat-resistant polymers typified by engineering plastics have been developed, the processing and use temperatures of the polymers have also been rising. To make these heat-resistant polymers flame retardant, a flame retardant is required that is thermally stable even at the temperatures at which the polymers are processed and used.

In addition, there is a need for a high-performance flame retardant that will not cause migration of flame retardant during processing such as injection molding, causing mold coating, and will not cause flame retardant bloom on the resin surface during long-term use of molded products. .

An object of the present invention is to provide a flame retardant particularly excellent in heat resistance and migration resistance.

[Means for solving the problems] In view of the above circumstances, the present inventors synthesized various compounds,
As a result of intensive research into new compounds that can be suitably used as flame retardants with excellent heat resistance and migration resistance, we found that
The present invention was achieved by discovering that a specific halogen-containing compound satisfies these conditions.

That is, in the present invention, in the general formula [IF (formula N), X represents a halogen atom, and a and d are 1
The present invention relates to HPPE represented by a number from 1 to 5, b and c are numbers from 1 to 4) and a flame-retardant polymer composition containing the same.

The HPPE of the present invention is a novel compound having a chemical structural formula represented by the general formula N], and exhibits a halogen H content, a melting point, and an infrared absorption spectrum as described below.

X in the general formula represents a halogen atom, and is chlorine or bromine, but chlorine and bromine may be mixed in the same molecule.

Specific examples of the compound represented by the general formula [I] of the present invention include tetrabromobis(4-phenoquinphenyl)ether, pentabromobis(4-phenoxyphenyl)
Ether, hexabromobis(4-phenoxyphenyl)ether, heptabromobis(4-phenoxyphenyl)ether, octabromobis(4-phenoxyphenyl)ether, nonabromobis(4-phenoxyphenyl)ether, decabromobis(4-phenoxyphenyl) ) ether, undecabromo bis(4-phenoxyphenyl) ether, dodecabromo bis(4-phenoxyphenyl) ether, tridecabromo bis(4-phenoxyphenyl) nityl, tetradecabromo bis(4-phenoxyphenyl) ether,
-phenoxyphenyl) ether, pentadecabromobis(4-phenoxyphenyl)ether, hexadecabromobis(4-phenoxyphenyl)ether, heptadecabromobis(4-phenoxyphenyl)ether,
Bromine compounds such as octadecabromobis(4-phenoxyphenyl)ether, tetrachlorobis(4-phenoxyphenyl)ether, pentachlorobis(4-phenoquinphenyl)ether, hexachlorobis(4-phenoxyphenyl)ether, heptachlorobis(4-phenoxyphenyl)ether, Chlorobis(4-phenoxyphenyl)ether, octachlorobis(4-phenoxyphenyl)ether, nonachlorobis(4-phenoxyphenyl)ether, decachlorobis(4-phenoxyphenyl)ether, undecachlorobis(4-phenoxyphenyl)ether
-phenoxyphenyl) ether, dodecachlorobis(
4-phenoxyphenyl) ether, tridecachlorobis(4-phenoxyphenyl)ether, tetradecaryrolobis(4-phenoxyphenyl)ether, pentadecachlorobis(4-phenoxyphenyl)ether,
These are chlorine compounds such as hexadecalyrolobis(4-phenoxyphenyl)ether, heptadecalyrolobis(4-phenoxyphenyl)ether, and octadeclyrolobis(4-phenoxyphenyl)ether, and mixtures thereof may also be used.

Next, the production of HPPE of the present invention involves halogenating bis(4-phenoxyphenyl)ether with a saponification reagent such as bromine, a brominating agent, chlorine, or a chlorinating agent in the presence of a suitable catalyst. This can be achieved by The degree of halogenation is
It can be controlled by the amount of halogenating reagent and the type of Lewis acid catalyst.

The polymer compounds whose flame retardance can be improved by the novel compound of the present invention are not particularly limited, but include, for example, polyethylene, polypropylene, polybutene, polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-ethyl Acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-grafted vinyl chloride copolymer, ethylene-ethyl acrylate-grafted vinyl chloride copolymer polymer, ethylene-propylene-grafted vinyl chloride copolymer, chlorinated polyethylene, chlorinated polyethylene-grafted vinyl chloride copolymer,
Polystyrene, ABS.

Thermosetting of thermoplastic resins or elastomers such as acrylic resin, polymethyl methacrylate, polyamide, polycarbonate, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, unsaturated polyester, polyurethane, epoxy resin, phenolic resin, melamine resin, urea resin, etc. Examples include rubber resins, butyl rubber, chloroprene rubber, nitrile rubber, natural rubber, silicone rubber, chlorosulfonated polyethylene, styrene-butadiene rubber, and polyester-ether elastomer. These polymers may be used alone or in combination of two or more.

The amount of the flame retardant of the present invention added varies depending on each target polymer compound, but is usually 1 part by weight or more, preferably 1 to 100 parts by weight, per 100 parts by weight of the polymer compound.

The method of adding the flame retardant of the present invention to the polymer compound is arbitrary and not particularly specified, but for example, a method of mixing the polymer and the flame retardant together in the form of chips or powder, a method of melt-molding the mixture, Alternatively, the polymer and the flame retardant may be put into a solution state, mixed, and then reprecipitated with a poor solvent, or the solvent may be evaporated.

Furthermore, when using the novel compound of the present invention as a flame retardant,
In order to enhance the flame retardant effect, a flame retardant aid such as antimony trioxide or other known flame retardants may be used in combination. Further, known additives such as antioxidants, colorants, ultraviolet absorbers, stabilizers, fillers, and antistatic agents can also be used.

[Effects of the Invention] The novel compound of the present invention imparts excellent flame retardancy to polymer compounds. It also has excellent heat resistance, and the weight loss temperature at 5% heating is 390°C or higher, so it can be applied to most polymeric compounds, and no thermal decomposition or evaporation is observed during molding.

Furthermore, since no blooming of the compound on the polymer surface is observed after the molding process, stable flame retardant properties can be exhibited over a long period of time.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

(Example 1) Synthesis of octadecabromobis(4-phenoxyphenyl)ether 69.3 g of bromine was placed in a 200 ml round bottom flask equipped with a cooling condenser with a hydrogen bromide trap and a stirring blade.
, 40 ml of 1,2-dichloroethane and 0.4 g of aluminum chloride were added, and the mixture was heated to 50°C and stirred. Next, a solution prepared by dissolving 4.26 g of bis(4-phenoxyphenyl)ether in 80 ml of 1,2-dichloroethane was added dropwise to this bromine solution over 2.3 hours. Subsequently, the reaction solution was heated, refluxed with bromine, and aged for 2.5 hours under flowing conditions.

After the reaction was completed, the mixture was cooled to room temperature, 80 ml of water was added, and bromine and 1,2-dichloroethane were distilled off by heating.

After cooling, the slurry was filtered and washed with water.
After drying at 50° C. for 6 hours, 20°68 g of a white solid was obtained. (Yield 97.1%) From the analysis results below, it was confirmed that it was octadecabromobis(4-phenoxyphenyl)ether. In addition, the thermal stability of this compound was determined by thermogravimetric analysis (TGA).
The results are also shown.

Elemental analysis value Actual value (%) Theoretical value (%) C-16,3116,24 H-<0.05 0.00 Br-81,1081,05 Melting point * 1 375°C Mass spectrometry spectrum Mass (m/e) 1774 (M+) Thermogravimetric analysis *2 Heating weight loss (weight%) Temperature ("C) *1; By differential thermal analysis *2; Analysis conditions Atmosphere Air gas flow rate 30.5 ml/min Heating rate 10°C/m i n Measurement temperature Room temperature to 500°C (Example 2) Synthesis of decabromobis(4-phenoxyphenyl)ether A 3fI round bottom flask equipped with a cooling condenser with a hydrogen bromide trap and a stirring blade was charged with dichloromethane 80°C.
0ml, bis(4-phenoquinphenyl)ether 90. og and 1.89 g of iron powder were added, heated and stirred. 487.6 g of bromine was added dropwise to the solution under reflux at 40° C. over 7 hours, and then aged at the same temperature for 1 hour.

After the reaction was completed, the mixture was cooled to room temperature, 1 g of water was added, and bromine and dichloromethane were distilled off by heating.

After cooling, the resulting slurry was filtered, washed with water, and recrystallized with chloroform to obtain 268.8 g of a white solid. Star. (Yield 92.6%) From the analysis results described above, it was confirmed that it was decabromobis(4-phenoquinphenyl)ether.

In addition, the results of determining Δp1 of the thermal stability of this compound by thermogravimetric analysis (TGA) are also shown.

Actual elemental analysis value (%) Theoretical value (%) C-25,3025,21 H-0,720,71 Br=69.75 69.88 Melting point 249-253°C Mass spectrometry spectrum Mass (m/e) 1143 (M+) Thermogravimetric analysis Heating weight loss (wt%) Temperature (''C) (Example 3) Synthesis of octabromobis(4-phenoxyphenyl) ether 1Ω round equipped with a cooling condenser with a hydrogen bromide trap and a stirring blade 650 g of bromine and 15.19 g of antimony pentachloride were placed in a bottom flask, heated and stirred.59
A solution prepared by dissolving 90.0 g of bis(4-phenoxyphenyl) ether in 180 ml of chloroform was added dropwise to the solution under reflux under heating at .degree. C. over 3 hours, and then aged at the same temperature for 1 hour. After the reaction is complete, cool to room temperature and add 300ml of water.
1 was added and heated to distill off bromine and chloroform.

After cooling, the resulting slurry was filtered and washed with water to obtain 249.0 g of a white solid.

From the analysis results below, it was confirmed that it was octabromobis(4-phenoxyphenyl)ether. In addition, the results of measuring the thermal stability of the present compound by thermogravimetric analysis (TGA) are also shown.

Elemental analysis value Actual A11l value (%) Theoretical value (%) C-29,4529,25 H-0,951,02 Br-64,5964,86 Melting point 217-228℃ Mass spectrometry spectrum M s s (m/e ) 9g5 (M
+) Thermogravimetric analysis heating! Tf amount reduction (wt%) Temperature ("C) (Example 4
-9 and Comparative Examples 1-2) Examples of using the compounds obtained in Examples 1-3 as flame retardants Polypropylene (7014 to Chisso, impact resistant grade)
Compounding agents were added to the pellets so that the compositions shown in Table 1 were obtained. In addition, the compounding amount unit of each component in each of the following examples is parts by weight.

The formulation was mixed for 12 minutes at 180'C.

Press the kneaded material at 200℃ for 2 minutes (100kg/am
2) L, under pressure at 30°C (100lc g/cm2)
Cool for 5 minutes and make sheets of 1 and 3 mm thick!・Molded into.

The mechanical properties and flame retardance of the obtained sheet were determined according to JISK 675.
8 and oxygen index measurement (J Is K7201).

The oxygen index method involves burning a sample in a controlled mixed gas of oxygen and nitrogen, emitting a candle-shaped flame, measuring the critical oxygen concentration (%) at the point of burning, and displaying this value as an index. It's a method.

The smaller the oxygen index value, the easier it is to burn, and the larger the value, the less flammable it is.

Further, the sheet was exposed to water at 160° C. for 100 hours, and the heat resistance was evaluated based on the color difference ΔE before and after exposure.

Further, after the sheet was left at 25° C. for 100 days, the presence or absence of flame retardant bloom was visually observed.

The results obtained are shown in Table 1.

(Example 10) Example of use of the compound obtained in Example 1 as a flame retardant High impact resistant polystyrene resin (Idemitsu Styrene HT50
) 15 parts by weight of the compound obtained in Example 1 and 5 parts by weight of antimony trioxide were added to 100 Lrrm parts on a mixing roll 2.
Knead at 10℃, heat press at 230℃ (100kg
/cm2)L and thicknesses of 1 and 3 rn m.

The mechanical properties and flame retardance of the obtained sheet were determined according to JISK7113.
and the oxygen index was determined by all standard (JIS K7201).

After the sheet was left at 25° C. for 100 days, the presence or absence of flame retardant bloom was visually observed.

The results obtained are shown in Table 2.

(Comparative Example 3.4) Based on Example 10, the same amount of the general-purpose elemental flame retardant decabromodiphenyl ether (DBDIE) as in the case where no flame retardant was added to the high-impact polystyrene resin (Comparative Example 3) For the case of blending (Comparative Example 4), i11+1 constant was conducted. The results obtained are shown in Table 2.

As shown in Table 2 and in the Examples, it was found that a flame retardant with excellent heat resistance and migration resistance was obtained.

[Brief explanation of the drawing]

1 to 3 are infrared absorption spectrum charts of the compounds of Examples 1 to 3, respectively.

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula [I], X represents a halogen atom, and a and d are 1
5, b and c are numbers 1 to 4). (2) A flame-retardant polymer composition characterized by blending a halogenated bis(4-phenoxyphenyl) ether represented by the general formula [I] into a polymer.