JPH02121941A - Halogenated trisphenyl derivative and flame retardant thermoplastic resin composition - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R1 to R3 are allyl, methallyl or 1-4C halogenated alkyl; X is halogen). EXAMPLE:1,1,1-Tris[4-allyloxy-3,5-dibromophenyl]ethane. USE:An addition type flame retardant for thermoplastic resins, especially styrene- based or polyolefin resins, above all, polypropylene resin without impairing mechanical properties of resin products and causing blooming problems. PREPARATION:The corresponding halogenated trisphenol type compound is reacted and etherified with allyl chloride or bromide or methallyl chloride, etc., by a conventional method and the resultant ether is then halogenated or the corresponding trishalogenated phenol type compound is reacted with a 1-4C halogenated hydrocarbon having >=2 halogens according to a conventional method to afford the compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a halogenated triphenyl derivative and a thermoplastic resin composition containing the halogenated triphenyl derivative and having excellent flame retardancy.

[Prior art] Generally, methods for imparting flame retardancy to thermoplastic resins include:
There are two main methods: a method of adding and mixing a flame retardant to a resin, and a method of 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 addition of flame retardants may reduce the mechanical properties, heat resistance, and transparency of resin products, and the flame retardants may bloom on the product surface. Particularly in polyolefin resins, especially polypropylene resins, blooming of flame retardants is a problem, and no satisfactory flame retardant has yet been found. Kawaishi, Hiss is said to be the most effective against the blooming problem and has a high flame retardant effect [3,
5-dibromo-4-(2',3゜dibromopropoxy)
Although phenyl]sulfone tends to bloom on the product surface to a lesser extent than other flame retardants, the problem of bleed-out that 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 provides a halogenated triphenyl derivative represented by the general formula (1) and a flame-retardant thermoplastic resin obtained by incorporating the halogenated triphenyl derivative into a thermoplastic resin to exhibit flame retardancy. This relates to a composition.

In the above general formula, R1, R2 and R3 are preferably halogenated alkyl groups having 1 to 4 carbon atoms, and particularly preferably brominated alkyl groups having 3 to 4 carbon atoms. Further, X is preferably a bromine atom or a chlorine atom, particularly preferably a bromine atom alone.

Specific examples of the compound represented by the above general formula (i>) include: α α 5" Br CH2 -CI = CH2 CH2 CH3 -C=CH2 death etc.

The compound represented by the above general formula (I>) 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 by a conventional method. It can also be produced by reacting the 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 the thermoplastic resin that imparts flame retardance by containing the compound represented by the general formula (I) include polyolefin resins such as polyethylene and polypropylene, polystyrene, high impact polystyrene, AS resin, ABS resin, AAs resin, AC3 resin, styrene resin such as AES resin, nylon 6, nylon 6/6
Polyamide resins such as polyethylene terephthalate.

Examples include polyester resins such as polybutylene phthalate, polysulfone resins, polyacetal resins, polycarbonate resins, and polyphenylene ether resins.

Among these resins, polyolefin resins and styrene resins are particularly preferred because the compound represented by the general formula (I) imparts excellent flame retardancy and mechanical properties. Among polyolefin resins, polypropylene resins are particularly preferred. The compound represented by the general formula (I) 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 (I>) 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 (I>) varies depending on the type of the target thermoplastic resin and the flame retardance required, etc. - Although it cannot be generally specified, it is usually 100% of the thermoplastic resin.
The amount is appropriately selected in the range of 0.5 to 80 parts by weight, and a particularly preferable range is 1 to 40 parts by weight. If the compound of general formula (I>) exceeds 80 parts by weight, it will adversely affect the mechanical properties of the resin product. If it is less than 0.5 parts by weight, a sufficient flame retardant effect will not 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. Such halogen flame retardants include, for example, 2,2-bis[3,5-dibromo-4-(2°, 3°-dibromo[propoxy)phenyl]propane, bis[3,5di10mo-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, brominated hisphenol oligocarbonate, brominated bisphenol epoxy resin, bromine Examples include chemically modified polystyrene.

In addition, phosphorus flame retardants, antimony oxide,
Even if flame retardant aids such as molybdenum oxide, fillers such as aluminum hydroxide, talc, calcium carbonate, titanium oxide, silica, alumina, mica, and calcium sulfate, and reinforcing fillers such as glass fiber and carbon lli fiber are added. Well also antioxidants, anti-aging agents, stabilizers, UV absorbers, lubricants,
It may also contain an effective amount of a mold release agent, pigment, etc.

What about the flame-retardant thermoplastic resin composition of the present invention? ! Any blending method can be used to create the compound. For example, it can be produced by mixing thermoplastic resin powder or pellets and the compound of general formula (I) in a tumbler-9 type blender, etc., and then melting and blending them in an extruder, roll, etc.

The flame-retardant thermoplastic resin composition thus obtained is made into a molded article by injection molding, extrusion molding, compression molding, or the like.

[Effects of the Invention] When the halogenated triphenyl derivative of the present invention is blended into a thermoplastic resin, it can impart excellent flame retardancy without deteriorating its properties, and furthermore, it can provide excellent flame retardancy, which has been a serious problem in the past. It does not cause any blooming, and does not cause blooming even in polypropylene resin, which is particularly prone to blooming, and its effects are exceptional.

[Example] The present invention will be described in detail with reference to Examples below.

Example 1 Production of phenyl]ethane In a reaction vessel equipped with a stirring device, a thermometer, and a reflux condenser, 1.
1.1-- Tris(3,5-dibromo-4-hydroxyphenyl)ethane 116.9(] (0.15mol
) and 19.2C of sodium hydroxide in 120g of water.
A solution of I (0.48 mol) was added, followed by 480 g of methyl alcohol. After adding grill bromide 58.1c+ (0.48 mol) with stirring,
Stirred at 5-60'C for 4 hours. After cooling, the product was separated, washed with water, washed with methyl alcohol, and then dried. Melting point 1
Solid at 60-165℃ 107.4(] (yield 79,
6%) was obtained. Bromine content of the product was 53.1% (theoretical value 53.3%).

The product was confirmed to be 1.1.1-tris(4-allyloxy-3,5-dibromophenyl)ethane (hereinafter referred to as compound A) by infrared absorption spectroscopy and NMR analysis.

The infrared absorption spectrum is shown in Figure 1, and the NMR analysis results are shown in Figure 2.
Shown in the figure.

(q compound A89.9Q (0.10 mol)
a stirring device.

The mixture was placed in a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel, and 720 (l) of methylene chloride was added and dissolved. While stirring and maintaining the temperature at 20°C, bromine (49.5 (1 (0)
, 31 mol) was added dropwise. 38-40' after dropping bromine
The reaction was completed by stirring at C for 1.5 hours. 2% after cooling
It was neutralized with an aqueous sodium hydroxide solution, and then washed with water five times. For one trigram, methyl alcohol of the same weight and weight was added to the methylene chloride solution with stirring to crystallize the product) and dried separately. 113.1 g (yield: 82.0%) of a solid having a melting point of 77 to 80° C. was obtained.

Bromine content of the product was 69.1% (theoretical value 69.5%).

Infrared absorption spectroscopy and NMR analysis revealed that the product was 1.1.1-tris[3,5-dibromo-4-
It was confirmed that it was (2°,3'-dibromopropoxy)phenyl]ethane (hereinafter referred to as compound B).

The infrared absorption spectrum is shown in FIG. 3, and the NMR analysis results are shown in FIG. 4.

Example 2 Polypropylene resin [Chisso ■ Chisso Polypro 170
19] 100 parts by weight 2 Small parts of compound B5 obtained in Example 1, Niandimon dioxide [ATOX-3 manufactured by Nippon Shinko ■]
After adding and mixing 2.5 weight omega parts, the mixture 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 part of 1 g at 200°C. (The following test was conducted on the qRada test piece.

0.1. ...0.1. (Oxygen index) is ASTH028
63.

Blooming test: Appearance was visually evaluated after being left at 80°C for 120 hours.

As shown in Table 1, the test results obtained for 1q showed excellent flame retardancy and no blooming of the flame retardant was observed.

Example 3 In Example 2, the compound obtained in Example 1 was used in Example 2 except that 310 parts of the seriously injured part and 5 parts of diantimony trioxide were used.
The test was conducted in the same manner.

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, 85 parts by weight of the 10 compound in Example 1, 2,2-bis[3,5-dibromo-4-(2').

The test was carried out in the same manner as in Example 2, except that 3'-dibromopropoxy)finyl]propane [FGI13100 manufactured by Teijin Kasei ■] 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.

Comparative Example 1 In Example 2, 1q of Compound B in Example 1 was replaced with 5-fold ω parts of 2,2-bis[3,5-dibromo-4-(23-dibromopropoxyphenyl]propane). The test was conducted in the same manner as in Example 2.

As shown in Table 1, the test results showed excellent flame retardancy, but blooming was observed.

Table Examples 5 and 6 and Comparative Example 2 Polystyrene resin [Mitsubishi-EN Santo Kasei (Taisei Dialex HH-102) 100% compound ¥IIJA obtained in Example 1 was added to the cloth shown in Table 2. After mixing,
The pellets were pelletized at 200° C. in the molding section 11a using an extruder.

The obtained pellet was molded at a temperature of 180 using an index molding machine.
The specimens were molded at °C.

The 1q test piece was subjected to the same specific viscosity test as in Example 2 at 0.1° and the following specific viscosity.

Specific viscosity: 1 g of sample was dissolved in 100 ndl of toluene, and the specific viscosity was measured at 30° C. Test results are shown in Table 2.

table

[Brief explanation of the drawing]

Figure 1 shows the red Tato absorption spectrum of Compound A of Example 1.
Figure 2 is the NMR chart of compound A, Figure 3 is the NMR chart of compound B.
Figure 4 shows the NMR spectrum of compound B.
- It is.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, in the formula, R_1, R_2, and R_3 are the same or different allyl groups, methallyl groups, or It represents a halogenated alkyl group having 1 to 4 carbon atoms, and X represents the same or different halogen atoms. ] A halogenated triphenyl derivative represented by 2. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [However, in the formula, R_1, R_2, and R_3 are the same or different allyl groups, methallyl groups, or carbon atoms of 1 to 4. It 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 triphenyl derivative represented by the following in an amount exhibiting flame retardancy.