JPH0581575B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a halogenated trisphenyl derivative and a thermoplastic resin composition containing the halogenated trisphenyl derivative and having excellent flame retardancy. [Prior Art] Generally, methods for imparting flame retardancy to thermoplastic resins include adding and mixing a flame retardant to the resin;
There are two main methods: modifying the resin itself using a reactive flame retardant. Conventionally, various types of flame retardants added to thermoplastic resins have been known, but these types of flame retardants have many drawbacks. For example, the mechanical properties, heat resistance, and transparency of resin products decrease due to the addition of flame retardants, and the flame retardants bloom on the product surface. In particular, blooming of flame retardants is remarkable in polyolefin resins, especially polypropylene resins, and no satisfactory flame retardant has yet been found. Bis[3,5-dibromo-4-(2',
Although 3'-dibromopropoxy)phenyl]sulfone blooms onto the surface of the product in a small amount compared to other flame retardants, the disadvantage that it bleeds out and impairs the appearance of the product remains essentially unsolved. [Object of the Invention] The object of the present invention is to provide an additive flame retardant that does not impair the mechanical properties of resin products and does not cause blooming problems, and that the flame retardant can be used in thermoplastic resins, especially styrene resins, The object of the present invention is to provide a flame-retardant thermoplastic resin composition containing a polyolefin resin, especially a polypropylene resin. [Structure of the invention] The present invention is based on the general formula ()

[Chemical formula] However, in the formula, R ₁ , R ₂ , and R ₃ are each the same or different allyl group, methallyl group, or carbon number 1 to 4
represents a halogenated alkyl group, and X represents the same or different halogen atoms. The present invention relates to a halogenated trisphenyl derivative represented by the following formula and a flame-retardant thermoplastic resin composition comprising a thermoplastic resin containing the halogenated trisphenyl derivative in an amount that exhibits flame retardancy. In the above general formula, R ₁ , R ₂ and R ₃ have 1 to 4 carbon atoms
A halogenated alkyl group is preferred, and a brominated alkyl group having 3 to 4 carbon atoms is particularly preferred.
Further, X is preferably a bromine atom or a chlorine atom, particularly preferably a bromine atom alone. Specific examples of compounds represented by the above general formula () include:

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

Examples include [C]. The compound represented by the above general formula () can be obtained by, for example, reacting a corresponding halogenated trisphenol type compound with allyl chloride, allyl bromide, methallyl chloride, etc. in a conventional manner to etherify the compound, and then etherifying this compound in a conventional manner. It can be produced by halogenation. It can also be produced by reacting a corresponding tris-halogenated phenol type compound with a halogenated hydrocarbon having two or more halogens and having 1 to 4 carbon atoms by a conventional method. Examples of thermoplastic resins that provide flame retardancy by containing a compound represented by the general formula () include polyolefin resins such as polyethylene and polypropylene, polystyrene, high impact polystyrene, AS resins, ABS resins, and AAS resins.
resin, styrene resin such as ACS resin, AES resin, polyamide resin such as nylon 6, nylon 6/6, polyester resin such as polyethylene terephthalate, polybutylene phthalate,
Examples include polysulfone resin, polyacetal resin, polycarbonate resin, and polyphenylene ether resin. Among these resins, polyolefin resins and styrene resins are particularly preferred because the compound represented by the general formula () imparts excellent flame retardancy and mechanical properties. Among polyolefin resins, polypropylene resins are particularly preferred. The compound represented by formula () not only provides sufficient flame retardancy but also has the great advantage of solving the blooming problem. Compounds (1) or (4) in the above-mentioned examples of compounds of general formula () are most suitable for solving the blooming problem of polypropylene resins while imparting sufficient flame retardancy. The amount of the compound represented by the above general formula () varies depending on the type of thermoplastic resin to be used and the flame retardance required, and cannot be determined unconditionally, but it is usually 0.5 parts by weight per 100 parts by weight of the thermoplastic resin. 80 parts by weight, and a particularly preferable range is 1 to 80 parts by weight.
It is 40 parts by weight. If the compound of general formula () exceeds 80 parts by weight, it will adversely affect the mechanical properties of the resin product. If the amount is less than 0.5 part by weight, sufficient flame retardant effect cannot be obtained. The flame-retardant thermoplastic resin composition of the present invention may be used in combination with a commonly used halogen-based flame retardant. Examples of such halogen flame retardants include 2,2
-bis[3,5-dibromo-4-(2',3'-dibromopropoxy)phenyl]propane, bis[3,5-dibromo-4-(2',3'-dibromopropoxy)phenyl]sulfone, 2 ,2-bis(4
-Allyloxy-3,5-dibromophenyl)propane, bis(4-allyloxy-3,5-dibromophenyl)sulfone, tris(2,3-dibromopropyl)isocyanurate, brominated diphenyl ether compound, bromination Examples include bisphenol oligocarbonate, brominated bisphenol epoxy resin, and brominated polystyrene. In addition, as necessary, phosphorus flame retardants, flame retardant aids such as antimony oxide and molybdenum oxide, fillers such as aluminum hydroxide, talc, calcium carbonate, titanium oxide, silica, alumina mica, and calcium sulfate, glass fiber, A reinforcing filler such as carbon fiber may be added, and antioxidants, anti-aging agents, stabilizers, ultraviolet absorbers, lubricants, mold release agents, pigments, etc. may also be included in effective amounts. Any blending method can be used to produce the flame retardant thermoplastic resin composition of the present invention. For example, it can be produced by mixing thermoplastic resin powder or pellets and the compound of the general formula () using a tumbler, V-type blender, etc., and then melting and blending using an extruder, roll, etc. The thus obtained flame-retardant thermoplastic resin composition is molded into a molded article by injection molding, extrusion molding, compression molding, or the like. [Effect of the invention] The halogenated trisphenyl derivative of the present invention is
When blended into thermoplastic resins, it can impart excellent flame retardancy without reducing its properties, and it also does not cause blooming, which has been a serious problem in the past, and can be used in polypropylene resins, which are particularly prone to blooming. It does not cause blooming and the effect it produces is exceptional. [Example] The present invention will be described in detail with reference to Examples below. Example 1 1,1,1,-tris[4-allyloxy-3,
5-dibromophenyl]ethane and 1,1,
1,-Tris[3,5-dibromo-4-(2',
Production of 3'-dibromopropoxy)phenyl]ethane 1,1,1-tris(3,5-dibromo-4
-Hydroxyphenyl)ethane 116.9g
(0.15mol) of sodium hydroxide in 120g of water.
A solution of 19.2 g (0.48 mol) was added, followed by 480 g of methyl alcohol. After adding 58.1 g (0.48 mol) of allyl bromide under stirring, the temperature was increased to 55-60℃.
The mixture was stirred for 4 hours. After cooling, the product was separated, washed with water, washed with methyl alcohol, and then dried. Melting point 160
107.4 g (yield 79.6%) of solid at ~165°C was obtained. Bromine content of the product 53.1% (logical value 53.3%). Infrared absorption spectroscopy and NMR analysis revealed that the product was 1,1,1-tris(4-allyloxy-3,5-dibromophenyl)ethane (hereinafter referred to as
It was confirmed that the compound was compound A). The infrared absorption spectrum is shown in Figure 1, and the NMR analysis results are shown in Figure 2. 89.9 g (0.10 mol) of the obtained compound A was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and after adding and dissolving 720 g of methylene chloride, the mixture was stirred while maintaining the temperature at 20°C. ,bromine
49.5g (0.31mol) was added dropwise. 38 after dropping bromine
The reaction was completed by stirring at ˜40° C. for 1.5 hours. After cooling, it was neutralized with a 2% aqueous sodium hydroxide solution, and then washed with water five times. Thereafter, the same weight of methyl alcohol was added to the methylene chloride solution with stirring to crystallize the product, which was separated and dried. Melting point 77~80℃
113.1g (yield 82.0%) of solid was obtained. Bromine content of the product 69.1% (logical value 69.5%). Infrared absorption spectroscopy and NMR analysis revealed that the product was 1,1,1-tris[3,5-dibromo-4-(2',3'-dibromopropoxy)phenyl]ethane (hereinafter referred to as compound B). ). The infrared absorption spectrum is shown in Figure 3, and the NMR analysis results are shown in Figure 4. Example 2 Compound B5 obtained in Example 1 was added to 100 parts by weight of polypropylene resin [Chitsuso Polypro K-7019]
Part by weight, diantimony trioxide [manufactured by Nippon Seiko Co., Ltd.]
After adding and mixing 2.5 parts by weight of [ATOX-S], the mixture was pelletized using an extruder at a molding temperature of 200°C.
The obtained pellets are molded using an injection molding machine at
Test pieces were molded at 200°C. The following tests were conducted on the obtained test pieces. OI...OI (oxygen index) was determined according to ASTM D2863. Blooming test: Appearance was visually evaluated after being left at 80℃ for 120 hours. As shown in Table 1, the obtained test results showed excellent flame retardancy and no blooming of the flame retardant was observed. Example 3 In Example 2, compound B10 obtained in Example 1
The test was conducted in the same manner as in Example 2 except that 5 parts by weight and 5 parts by weight of diantimony trioxide were used. As shown in Table 1, the test results showed excellent flame retardancy and no blooming of the flame retardant was observed. Example 4 In Example 2, compound B5 obtained in Example 1
Parts by weight, 2,2-bis[3,5-dibromo-4-
The test was conducted in the same manner as in Example 2, except that 5 parts by weight of (2',3'-dibromopropoxy)phenyl]propane [FG#3100 manufactured by Teijin Kasei Ltd.] and 5 parts by weight of diantimony trioxide were used. Ivy. As shown in Table 1, the test results showed excellent flame retardancy, and no blooming of the flame retardant was observed. Comparative Example 1 In Example 2, 2,2-bis[3,5-dibromo-4-
The test was conducted in the same manner as in Example 2, except that 5 parts by weight of (2,3-dibromopropoxyphenyl)propane was used. The test results are shown in Table 1, although the flame retardance was excellent. , blooming was observed.

[Table] Examples 5, 6 and Comparative Example 2 Compound A obtained in Example 1 was added to 100 parts by weight of polystyrene resin [Dialex HH-102 manufactured by Mitsubishi Monsanto Chemical Co., Ltd.] in the amount shown in Table 2 and mixed. Thereafter, it was pelletized using an extruder at a molding temperature of 200°C. The obtained pellets were molded into test pieces using an injection molding machine at a molding temperature of 180°C. The obtained test piece was subjected to the same OI and specific viscosity tests as in Example 2. Specific viscosity...Dissolve 1g of sample in 100ml of toluene,
Measurement of specific viscosity at 30℃ The test results are shown in Table 2.

【table】 [Brief explanation of the drawing]

Figure 1 is an infrared absorption spectrum of Compound A of Example 1, Figure 2 is an NMR chart of Compound A, and Figure 3 is an NMR chart of Compound A.
The figure shows the infrared absorption spectrum of Compound B, and Figure 4 shows the NMR chart of Compound B.

Claims (1)

[Claims] 1 General formula () [Chemical formula] However, in the formula, R ₁ , R ₂ , and R ₃ are each the same or different allyl group, methallyl group, or carbon number 1 to 4
represents a halogenated alkyl group, and X represents the same or different halogen atoms. A halogenated trisphenyl derivative represented by 2 General formula () [Chemical formula] However, in the formula, R ₁ , R ₂ , and R ₃ are each the same or different allyl group, methallyl group, or carbon number 1 to 4
represents a halogenated alkyl group, and X represents the same or different halogen atoms. A flame-retardant thermoplastic resin composition comprising a thermoplastic resin containing a halogenated trisphenyl derivative represented by the following in an amount exhibiting flame retardancy.