JP2000109445A - Bromine compound and flame-retarded resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retarded resin composition having excellent flame- retardancy, causing little color change in high-temperature melt processing and giving a molded article having good color tone by controlling the content of a specific impurity in a bromine compound to be used as a flame-retardant to or below a specific level. SOLUTION: The objective composition is composed of (A) 100 pts.wt. of a thermoplastic resin (e.g. polystyrene resin or polyolefin resin), (B) 1-50 pts.wt. of a bromine compound and (C) 0-25 pts.wt. of an inorganic flame-retarding assistant (e.g. antimony trioxide). The component B is composed mainly of a bromine compound of formula I (X is a halogen; (m) and (n) are each 1-6; (p) and (q) are each 0-10; p+q>=1; Ar1 and Ar2 are each a 5-6C aromatic hydrocarbon group or a 5-12C saturated alicyclic hydrocarbon group; Y is a 1-6C saturated hydrocarbon group or the like; R1 and R2 are each a 2-11C hydrocarbon group) e.g. 2,2-bis[3,5-dibromo-4-(2,3-dibromopropyloxy)phenyl]propane}. The amount of the bromine compound of formula II ((s) is 1-10) is <=0.02 mol based on 1 mol of the bromine compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bromine compound having excellent heat stability and a flame-retardant resin composition containing the bromine compound having a good hue.

[0002]

2. Description of the Related Art Organic polymer materials are used in various applications because of their excellent moldability, mechanical properties, and electrical properties. Among them, high impact polystyrene (HIPS) resins, styrene resins such as ABS resins and polyolefin resins are inexpensive in addition to excellent properties. It is widely used for various purposes including building materials and automotive parts.

[0003] Further, since these organic polymer materials are generally flammable, the burning of organic substances may cause disasters that threaten the safety of people, and it is necessary to take measures to make such organic polymer materials nonflammable. With regard to flame retardancy of organic polymer materials, various regulations, including UL standards, have been strengthened and required.

[0004] In general, the flame retardation of an organic polymer material is performed by adding a flame retardant to the organic polymer material, blending a flame retardant resin, and using a reactive flame retardant monomer. Is carried out by a method such as reforming.

[0005] As a flame retarding method for thermoplastic resins such as styrene-based resins and polyolefin-based resins, blending of various bromine compounds has been conventionally proposed. For example,
For the flame retardation of styrene resins, 2,2-bis [(3,5-dibromo-4-allyloxy) phenyl] propane (Japanese Patent Publication No. 60-8019) and hexabromocyclododecane (Japanese Patent Publication No. No. 43-29658) is known in such resins.
Such a flame retardant has a low decomposition temperature and, when kneaded with a resin and melt-molded, has a disadvantage that the thermal stability of the resin is greatly reduced, such as coloring of a molded product.

[0006] In order to improve such thermal stability, 2,2-bis [@ 3,5-dibromo-4-l- as a flame retardant.
(2,3-dibromopropyloxy) @phenyl] propane (JP-A-60-240750, etc.), bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone ( JP-A-60-24
No. 0750) is blended with such a styrenic resin, and 2,2-bis [@ 3,5-dibromo-4] is used as a flame retardant for making a polyolefin resin flame-retardant. -(2,3-dibromopropyloxy) @phenyl] propane (Japanese Patent Publication No. 5-82856, etc.),
Bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone (JP-B-50-
No. 35103) is known.

However, along with high-temperature molding and the like for improving molding efficiency, even a resin composition containing these bromine compounds has insufficient thermal stability, and further contains a bromine compound having improved thermal stability. There is a demand for a flame-retardant resin composition having excellent thermal stability.

[0008]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies with the aim of providing a flame-retardant thermoplastic resin composition having excellent thermal stability. By controlling the specific impurities contained in the resin to a specific amount or less, the change in color tone during high-temperature melt processing is small, and the color tone of the molded article is good, and a thermoplastic resin composition excellent in flame retardancy can be obtained. The present invention has been found.

[0009]

That is, according to the present invention, a bromine compound represented by the following general formula (1) is a main component, and the content of the bromine compound represented by the following general formula (2) is as follows: There is provided a bromine compound characterized by being at most 0.02 mol per mol of the bromine compound represented by the general formula (1).

[0010]

Embedded image

(Where X is a halogen atom, m and n are integers of 1 to 6, p and q are integers of 0 to 10 and p + q is 1 or more, and Ar ¹ and Ar ² are the same or different. May represent an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents 1
To 6 saturated hydrocarbon groups, sulfone groups, sulfide groups,
R ¹ and R ² are ^one selected from a ketone group, an alkylene oxide group having 2 to 6 carbon atoms and a single bond;
11 hydrocarbon groups. )

[0012]

Embedded image

(Where X, m, n, Ar ¹ , Ar ² ,
Y and R ¹ have the same meanings as defined in the general formula (1), and s is an integer of 1 to 10. Further, according to the present invention, (B) 1 to 50 parts by weight of a bromine compound and (C) 0 to 25 parts by weight of an inorganic flame retardant, based on 100 parts by weight of a thermoplastic resin, The bromine compound is mainly composed of the bromine compound represented by the general formula (1), and the content of the bromine compound represented by the general formula (2) is 1 mol of the bromine compound represented by the general formula (1). To 0.02 mol or less with respect to the flame-retardant resin composition.

The bromine compound of the present invention has the general formula (1)
And a bromine compound containing the bromine compound represented by the formula (1) in an amount of preferably at least 80% by weight, more preferably at least 85% by weight, particularly preferably at least 90% by weight.

X in the formula (1) is a halogen atom, preferably bromine, m and n are integers of 1 to 6, preferably 2 to 4, and p and q are integers of 0 to 10. And p + q is an integer of 1 or more, preferably p and q are integers of 2 to 10, Ar ¹ and Ar ² may be the same or different, and have an aromatic hydrocarbon group of 5 to 16 carbon atoms or carbon atom. It is a saturated alicyclic hydrocarbon group of the formulas 5 to 12, preferably a phenyl group, a tolyl group, a xylyl group or a naphthyl group. Y is one selected from a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms and a single bond, and is preferably methylene, isopropylidene, cyclohexylidene. It is one selected from den, sulfone, sulfide, ketone, and a single bond, and R ¹ and R ² are a hydrocarbon group having 2 to 11 carbon atoms, preferably a linear saturated hydrocarbon group.

As the bromine compound represented by the formula (1), specifically, 2,2-bis [3,5-dibromo-4]
-(2,3-dibromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3
-Dibromo-2-methylpropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,
3-dibromobutyloxy) phenyl] propane, 2,
2-bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3-dibromopentyloxy) phenyl] Propane, 2,2-bis [3,5-
Dibromo-4- (4,5-dibromopentyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (2,3,4,5-tetrabromopentyloxy)
Phenyl] propane;

Bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3- Dibromobutyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3-dibromopentyloxy) Phenyl] sulfone, bis [3,5-dibromo-4- (4,5-dibromopentyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3,4,5-tetrabromopentyloxy) ) Phenyl] sulfone;

1,1-bis [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3-
Dibromo-2-methylpropyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3-
Dibromobutyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- ( 2,3-dibromopentyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4-
(4,5-dibromopentyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3,
4,5-tetrabromopentyloxy) phenyl] ethane;

Bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane, bis [3,5
-Dibromo-4- (2,3-dibromobutyloxy) phenyl] methane, bis [3,5-dibromo-4- (3,
4-dibromobutyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromopentyloxy) phenyl] methane, bis [3,5-dibromo-
4- (4,5-dibromopentyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3,4,5
-Tetrabromopentyloxy) phenyl] methane;

[3,3 ', 5,5'-tetrabromo-
4,4'-di (1,2-dibromoethyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,
4'-di (2,3-dibromopropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'
-Di (2,3-dibromo-2-methylpropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'-di (2,3-dibromobutyloxy)]
Biphenyl, [3,3 ', 5,5'-tetrabromo-
4,4'-di (3,4-dibromobutyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,
4'-di (2,3-dibromopentyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'
-Di (4,5-dibromopentyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,4'-
Di (2,3,4,5-tetrabromopentyloxy)]
Biphenyl;

2,2-bis [4,6,8-tribromo-
5- (2,3-dibromopropyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3-dibromopropyloxy) β-naphthyl] propane, 2, 2-bis [4,6,8-tribromo-5- (2,3-dibromo-2-methylpropyloxy) α-naphthyl] propane, 2,2-bis [4,6
7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo -5- (3,4-dibromobutyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β-naphthyl] propane, , 2-bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3 -Dibromopentyloxy) β-naphthyl Propane, 2,2-bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- ( 4,5-dibromopentyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo-5- (2,3,4,5-tetrabromopentyloxy) α-naphthyl] propane,
2,2-bis [4,6,7-tribromo-5- (2,
3,4,5-tetrabromopentyloxy) β-naphthyl] propane;

Bis [4,6,8-tribromo-5-
(2,3-dibromopropyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (2
3-dibromopropyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5- (2,3-dibromo-2-methylpropyloxy) α-naphthyl] sulfone, bis [4,6,7 -Tribromo-5- (2,
3-dibromo-2-methylpropyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5-
(2,3-dibromobutyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (2,3
-Dibromobutyloxy) β-naphthyl] sulfone,
Bis [4,6,8-tribromo-5- (3,4-dibromobutyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β- Naphthyl] sulfone, bis [4,
6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] sulfone, bis [4,6,7
-Tribromo-5- (2,3-dibromopentyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α
-Naphthyl] sulfone, bis [4,6,7-tribromo-5- (4,5-dibromopentyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5
-(2,3,4,5-tetrabromopentyloxy) α
-Naphthyl] sulfone, bis [4,6,7-tribromo-5- (2,3,4,5-tetrabromopentyloxy) β-naphthyl] sulfone;

1,1-bis [4,6,8-tribromo-
5- (2,3-dibromopropyloxy) α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-
5- (2,3-dibromopropyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-
5- (2,3-dibromo-2-methylpropyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] ethane, 1,1-bis [4
6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] ethane, 1,1-bis [4,6
7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8
-Tribromo-5- (3,4-dibromobutyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β-
Naphthyl] ethane, 1,1-bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5 -(2,3-dibromopentyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] ethane, 1,1 -Bis [4,6,7-tribromo-
5- (4,5-dibromopentyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-
5- (2,3,4,5-tetrabromopentyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (2,3,4,5-tetrabromopentyloxy) β-naphthyl] ethane;

Bis [4,6,8-tribromo-5-
(2,3-dibromopropyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (2,3-
Dibromopropyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (2,3-dibromo-
2-methylpropyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] methane,
Bis [4,6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] methane, bis [4
6,7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (3,4-dibromobutyloxy) α-naphthyl] methane, Bis [4,6,7-tribromo-5-
(3,4-dibromobutyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] methane, bis [4,6,7- Tribromo-5- (2,3-dibromopentyloxy) β-naphthyl] methane, bis [4,6
8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (4,5-dibromopentyloxy) β-naphthyl] methane, bis [ 4,6,8-tribromo-5-
(2,3,4,5-tetrabromopentyloxy) α-
Naphthyl] methane, bis [4,6,7-tribromo-5
-(2,3,4,5-tetrabromopentyloxy) β
-Naphthyl] methane and the like.

Among them, 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane and 2,2-bis [3,5-dibromo-4-
(2,3-Dibromo-2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,
3-dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane, [3,3 ′,
5,5'-tetrabromo-4,4'-di (2,3-dibromopropyloxy)] biphenyl, [3,3 ', 5
5'-tetrabromo-4,4'-di (1,2-dibromoethyloxy)] biphenyl, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl]
Sulfone and bis [3,5-dibromo-4- (2,
3-dibromo-2-methylpropyloxy) phenyl]
Sulfone is preferred, and 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane and 2,2-bis [3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl] propane is more preferred, and 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane is particularly preferably used.

In the present invention, in the bromine compound containing the bromine compound represented by the general formula (1) as a main component, the content of the compound represented by the general formula (2) is controlled by the content of the general formula (1).
Is not more than 0.02 mol, preferably 0.0001 to 0.02 mol, and more preferably 0.1 mol to 1 mol of the bromine compound represented by the formula (1).
0001 to 0.018 mol is more preferred. When the content of the compound represented by the general formula (2) exceeds 0.02 mol with respect to 1 mol of the bromine compound represented by the formula (1), a resin composition obtained by blending the bromine compound with a thermoplastic resin Is unfavorable because the thermal stability of the polymer decreases.

The bromine compound 1 represented by the general formula (1)
The content (mole) of the compound represented by the above general formula (2) with respect to the mole was determined by high performance liquid chromatography.
Can be measured by a method of detecting absorption at 80 nm,
The peak area of the component of the bromine compound represented by the general formula (1) obtained from the same chromatography and the peak area of the compound represented by the general formula (2) are determined, and the area ratio is calculated. Can be Here, since the relative sensitivities of the bromine compound represented by the general formula (1) and the compound represented by the general formula (2) are close to each other, the area ratio can be defined as a molar ratio. The peak position of the compound represented by the general formula (2) is a peak that increases when the concentration of the compound represented by the following general formula (4) is increased during the bromination reaction. It appears at a position more polar than the peak of the bromine compound represented by the formula (1).

In the process of producing the compound represented by the general formula (2), a compound having an aliphatic unsaturated bond represented by the following general formula (3) is reacted with bromine, and the compound represented by the general formula (1) is reacted. When synthesizing a bromine compound represented by the following general formula (3), the above-described general formula (3) is obtained by reacting a bromine with an impurity having a hydroxyl group represented by the following general formula (4) contained in the compound having an aliphatic unsaturated bond. A by-product having a hydroxyl group represented by the formula (2) is produced. In addition, when water is present in the reaction solution during the bromination reaction, the ether bond of the compound represented by the above general formula (1) or the following general formula (3) is apt to be cleaved. A by-product having the indicated hydroxyl group is formed.

[0029]

Embedded image

(Where X is a halogen atom, m and n are integers of 1 to 6, Ar ¹ and Ar ² may be the same or different, and may be an aromatic hydrocarbon group having 5 to 16 carbon atoms or a carbon atom). Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms, and a single bond. R ³ and R ⁴ each have at least one aliphatic unsaturated group and have 2 carbon atoms.
To 11 hydrocarbon groups. )

[0031]

Embedded image

(Where X is a halogen atom, m and n are integers of 1 to 6, Ar ¹ and Ar ² may be the same or different, and may be an aromatic hydrocarbon group having 5 to 16 carbon atoms or carbon atom). Represents a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, a ketone group, an alkylene oxide group having 2 to 6 carbon atoms, and a single bond. R ³ is a hydrocarbon group having 2 to 11 carbon atoms having at least one aliphatic unsaturated group.) The compound represented by the above general formula (2) is a specific example. Include 2-[{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] -2-[(3,5-dibromo-4-hydroxy) phenyl] propane;
[{3,3 ', 5,5'-tetrabromo-4- (2,3
-Dibromopropyloxy) -4'-hydroxy {diphenyl] sulfone, 1-[{3,5-dibromo-4-
(2,3-dibromopropyloxy) @phenyl] -1
-[(3,5-dibromo-4-hydroxy) phenyl]
Methane, [3,3 ', 5,5'-tetrabromo-4-
(2,3-dibromopropyloxy) -4'-hydroxy] biphenyl and the like.

As a method for suppressing the by-product of the compound having a hydroxyl group represented by the general formula (2), for example, the purity is increased by recrystallization or the like, and the amount of impurities represented by the general formula (4) is reduced. A method in which a solution in which a compound having an aliphatic unsaturated bond represented by the general formula (3) is dissolved in a solvent inert to the reaction is mixed with bromine or a bromine solution, and the mixture is reacted to perform bromination. When a solution obtained by dissolving the compound having an aliphatic unsaturated bond shown in 3) in a solvent inert to the reaction is mixed with bromine or a bromine solution, and the mixture is reacted and brominated, the amount of water in the reaction solution is reduced. A method of reducing the amount to a very small amount can be adopted.

As a method for reducing the water content in the reaction solution, the compound having an aliphatic unsaturated bond represented by the above general formula (3) is sufficiently dried, and the solvent used is anhydrous calcium carbonate, Anhydrous calcium chloride, a method of contacting with anhydrous sodium sulfate, etc., if the solvent may change with alkali, contact mixing with sulfuric acid, phosphorus pentoxide,
There is a method of performing a contact treatment with a water adsorption desiccant such as molecular sieves, and a method of purifying the solvent by distillation. It is also necessary to prevent the water vapor from being mixed into the reaction tank.

However, in this method, in order to reduce the amount of water in the reaction solution to the extent that the obtained bromine compound and the resin composition containing the same have sufficient thermal stability, a solvent pretreatment or water There are also inconveniences, such as a device for removing odors and an increase in operational restrictions.

Accordingly, as a more preferable method for obtaining a bromine compound having reduced impurities represented by the above general formula (2), a compound having an aliphatic unsaturated bond represented by the above general formula (3) is not allowed to react. When a solution dissolved in an active solvent is mixed with bromine or a bromine solution, and the mixture is reacted and brominated, the compound having an aliphatic unsaturated bond is represented by the following general formula per 100 unsaturated groups: A method for producing a bromine compound to be reacted by using a compound having a hydroxyl group represented by (5) in an amount corresponding to 0.5 to 20 hydroxyl groups can be employed.

[0037]

Embedded image

(Wherein R ⁵ is a C 1 -C 4 valence)
6 is an aliphatic group, and u represents an integer of 1 to 4. In the method for producing a bromine compound, the compound having a specific hydroxyl group represented by the general formula (5) is caused to exist in the reaction solution, whereby the compound represented by the general formula (1) due to the water present in the reaction solution is obtained. The cleavage of the ether bond of the bromine compound is suppressed, and the by-product of the compound represented by the general formula (2) is suppressed. Further, the thermal stability produced by the reaction between the intermediate formed by the reaction of water and bromine with the aliphatic unsaturated group of the compound having an aliphatic unsaturated bond represented by the above general formula (3) is adversely affected. The formation of the compound to be provided is suppressed, and the intermediate formed by the reaction of the compound having a hydroxyl group represented by the general formula (5) with bromine forms an aliphatic unsaturated bond represented by the general formula (3). By-products generated by reacting with the aliphatic unsaturated group of the compound having no adverse effect on the thermal stability of the bromine compound, the resulting bromine compound and a resin composition containing the same are heat-stable. It will be good.

The compound having a hydroxyl group used in the method for producing a bromine compound is a compound represented by the above general formula (5), wherein R ⁵ is a 1 to 4 valent aliphatic group having 1 to 6 carbon atoms, It is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms and having 1 to 6 carbon atoms or an oxygen- or sulfur-containing saturated hydrocarbon group having 1 to 4 carbon atoms, and u is an integer of 1 to 4, preferably 1 to 4. It is an integer of 2. Specifically, methanol, ethanol, n-propanol, i-propanol, n-
Butanol, i-butanol, sec-butanol, t
tert-butanol, allyl alcohol, ethylene glycol and diethylene glycol, among which methanol, ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol and tert-butanol are preferred, and methanol, ethanol and i-propanol are particularly preferably used.

The compound having a hydroxyl group is preferably a compound having an aliphatic unsaturated bond represented by the above general formula (3) in which the number of hydroxyl groups is preferably 0.5 to 20 per 100 unsaturated groups. , More preferably 1 to 15, more preferably 1 to 10. Within this range, cleavage of the ether bond of the bromine compound represented by the above general formula (1) by water is suppressed, and a compound having an aliphatic unsaturated bond and an intermediate formed by the reaction of water and bromine are contained. And the intermediate compound produced by the reaction of the compound having a hydroxyl group with bromine reacts with a compound having an aliphatic unsaturated bond. Thus, the amount of by-products generated is small, and the resin composition containing the obtained bromine compound is preferable because it does not adversely affect the flame retardancy.

In the bromination reaction, as described above, the compound having a hydroxyl group represented by the general formula (5) is mixed with a solution of a compound having an aliphatic unsaturated bond and bromine or a solution obtained by mixing bromine solution. , The generation of the above-mentioned general formula (2), which is a by-product, is suppressed. However, if the amount of water present in such a mixed solution is too large, a large amount of the compound having the hydroxyl group is used in order to suppress a side reaction due to moisture. An intermediate produced by the reaction between the compound having bromine and the compound having bromine, a large amount of by-products produced by the reaction with the compound having an aliphatic unsaturated bond are generated, and the purity of the obtained bromine compound becomes insufficient. This will adversely affect the flame retardancy of the resin composition containing the compound in the resin. Therefore,
The concentration of water in a solution of the compound having an aliphatic unsaturated bond during the bromination reaction, bromine or a reaction solution substantially consisting of a bromine solution and a compound having a hydroxyl group,
For the compound having an aliphatic unsaturated bond represented by the general formula (3), an amount corresponding to 10 or less water molecules per 100 unsaturated groups is preferable, and 0.05 to 1
An amount corresponding to 0 is more preferable, and an amount corresponding to 0.05 to 5 is more preferable. Such a water content is measured by the Karl Fischer method.

The solvent used for dissolving the compound having an aliphatic unsaturated bond represented by the above general formula (3) in the method for producing a bromine compound needs to be inert to the reaction. Such a solvent is preferably as high as possible in solubility for the compound having an aliphatic unsaturated bond, but may be partially dissolved. That is, any bromine compound produced by the bromination reaction of the compound having an aliphatic unsaturated bond may be dissolved in the solvent.

Examples of such a solvent include halogen-containing hydrocarbon compounds such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, chlorobenzene, and acetone chloride, diethyl ether, and ethyl isopropyl. Examples include ether hydrocarbon compounds such as ether, tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, carbon disulfide, pentane and the like. Also, bromine can be used as a solvent. Among them, methylene chloride, chloroform,
Halogenated aliphatic hydrocarbons such as 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, and acetone chloride are preferred, methylene chloride and chloroform are more preferred, and methylene chloride is particularly preferred. These solvents are used alone or in combination of two or more.

In the method for producing a bromine compound,
Bromine or a bromine solution is used. As the solvent used in the bromine solution, the same solvent as described above is used, and in this case, the concentration of bromine is preferably in the range of 10 to 90% by weight.

In the method for producing a bromine compound, as a method for mixing a solution in which a compound having an aliphatic unsaturated bond is dissolved in a solvent inert to a reaction with bromine or a bromine solution, bromine or a bromine solution is mixed with a fatty acid. A method of adding and mixing a solution of a compound having an aliphatic unsaturated bond, a method of adding and mixing a solution of a compound having an aliphatic unsaturated bond to a bromine or bromine solution, or a method of mixing a bromine or a bromine solution with an aliphatic unsaturated bond And a solution of the compound having the formula (1) are simultaneously added to the reaction vessel and mixed.

The reaction temperature in the method for producing a bromine compound is preferably -20 ° C. or higher, more preferably 5 ° C. or higher, and the bromination reaction is not limited to normal pressure, and may be performed under increased or reduced pressure. it can. Further, at the time of the bromination reaction, a method of removing the reaction heat of the bromination by the heat of vaporization of the solvent or bromine can be adopted, and the vaporized vapor is cooled by a condenser or the like, liquefied, and returned to the reaction tank. That is, a refluxing method can be used.

In the method for producing the bromine compound, a so-called batch method may be employed, in which a predetermined amount is added to the reaction tank to terminate the bromination reaction, or the bromination reaction can be continuously performed. While a raw material is continuously introduced, a take-out port is provided in a part of the reaction tank to allow a part of the reaction solution to be led out and continuously taken out to another tank. Further, a part of the derived reaction solution may be circulated.

The amount of bromine used in the method for producing a bromine compound may be a sufficient molar ratio to the compound having an aliphatic unsaturated bond in order to obtain a desired bromine compound. The number of bromine molecules is preferably in the range of 1 to 5, more preferably 1 to 3, per unsaturated group in the compound having a saturated bond.

The bromine compound intended for the present invention is a high-purity aliphatic unsaturated compound represented by the general formula (3) obtained by removing the impurities represented by the general formula (4) by recrystallization as described above. A bromine compound produced by reacting a compound having a bond with bromine in the presence of a compound having a hydroxyl group represented by the general formula (5),
The bromine compound can contain a compound represented by the following general formula (6).

[0050]

Embedded image

(Where X is a halogen atom, m and n are integers of 1 to 6, p and q are integers of 0 to 10 and p + q is 1 or more, and Ar ¹ and Ar ² are the same or different. May represent an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents 1
To 6 saturated hydrocarbon groups, sulfone groups, sulfide groups,
R ¹ and R ² are ^one selected from a ketone group, an alkylene oxide group having 2 to 6 carbon atoms and a single bond;
11 is a hydrocarbon group, R ⁶ and R ⁷ are an aliphatic group having 1 to 6 carbon atoms, v and w are integers of 0 to 5, and v + w is 1
That is all. As described above, the intermediate represented by the reaction of the compound having the hydroxyl group represented by the general formula (5) with bromine forms the above-mentioned aliphatic unsaturated bond. It is a by-product formed by reacting with an aliphatic unsaturated group of a compound having the compound, and the by-product does not adversely affect the thermal stability of the bromine compound. The content of the compound represented by the general formula (6) is 0.0 to 1 mol of the bromine compound represented by the general formula (1).
1 to 0.2 mol is preferable, 0.01 to 0.15 mol is more preferable, 0.01 to 0.1 mol is further preferable, and 0.01 to 0.05 mol is particularly preferable. When the content of the compound represented by the general formula (6) is 0.2 mol or less based on 1 mol of the bromine compound represented by the general formula (1), the bromine compound is used as a flame retardant in a resin. It is preferable because it does not adversely affect the flame retardancy of the compounded resin composition.

The bromine compound 1 represented by the above general formula (1)
The content (mole) of the compound represented by the above general formula (6) with respect to the mole was determined by high performance liquid chromatography.
Can be measured by a method of detecting absorption at 80 nm,
The peak area of the component of the bromine compound represented by the general formula (1) obtained by the same chromatography and the peak area of the compound represented by the formula (6) are determined, and the area ratio is calculated. Can be Here, the bromine compound represented by the general formula (1) and the bromine compound represented by the general formula (6)
Since the relative sensitivity with the compound represented by is similar, this area ratio can be used as a molar ratio. The position of the peak of the compound represented by the general formula (6) is a peak that appears when a compound having a hydroxyl group represented by the general formula (5) is added during the bromination reaction.

As described above, the bromine compound of the present invention has good thermal stability and excellent handleability, and is useful as a stabilizer for γ-ray resistance and a flame retardant. Is a resin composition having good hue of the molded article and excellent flame retardancy.

The thermoplastic resin (A) used in the present invention includes, for example, polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene ether resin and the like. Among them, polyolefin resins and polystyrene resins are preferably used.

The polyolefin resin is a homopolymer or a copolymer of olefins such as ethylene, propylene and butene, or a copolymer with a component copolymerizable with these olefins. Polypropylene, ethylene-vinyl acetate copolymer,
Ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer and propylene-butene copolymer, etc. Among them, polypropylene is preferably used.

The polystyrene resin refers to a resin containing a vinyl aromatic monomer as a constituent component. Examples of the vinyl aromatic monomer include styrene, o-methylstyrene, and p-methylstyrene.
Nuclear alkyl-substituted styrenes such as -methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-tert-butylstyrene, and α-alkyls such as α-methylstyrene and α-methyl-p-methylstyrene Examples include a halogen-substituted styrene such as substituted styrene, monobromostyrene, dibromostyrene, and tribromostyrene. Specifically, polystyrene, polymethylstyrene, rubber-modified styrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acryl rubber-styrene copolymer Polymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), methyl methacrylate-butadiene-styrene copolymer (MBS
HIPS and ABS resins are preferable, and HIPS is particularly preferably used.

Such a rubber-modified styrene resin (HIPS)
The term "polymer" refers to a polymer in which a rubber-like polymer is dispersed in the form of particles in a matrix composed of a polystyrene resin, and in the presence of the rubber-like polymer, styrene and, if necessary, a vinyl monomer copolymerizable therewith. By subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization. The polymerization method may be one-stage polymerization or multi-stage polymerization. Examples of the diene rubber component forming this rubbery polymer include polybutadiene, polyisoprene, styrene-butadiene copolymer,
Rubbers such as butadiene-isoprene copolymer, ethylene-propylene copolymer, and natural rubber are preferably used, and the proportion is preferably 5 to 80% by weight in the HIPS resin component.

The ABS resin is a graft copolymer obtained by graft-polymerizing an aromatic vinyl compound component and a vinyl cyanide compound component capable of graft copolymerization with a diene rubber component as a base. Examples of the diene rubber component include polybutadiene and styrene-butadiene copolymer.Examples of the aromatic vinyl compound component grafted to these diene rubber components include styrene and α.
-Methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, among which styrene is preferably used, and examples of the vinyl cyanide compound component include acrylonitrile, methacrylonitrile, chloroacrylonitrile, and the like. Among them, acrylonitrile is preferably used.
Further, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, maleic anhydride, N-substituted maleimide and the like can be used. Such a graft copolymer,
It may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and the grafting method may be a single-stage graft or a multi-stage graft. Further, a blend of a vinyl copolymer obtained by separately copolymerizing the aromatic vinyl compound component and the vinyl cyanide compound component with a graft copolymer can also be preferably used.

These thermoplastic resins can be used alone or in combination of two or more.

The bromine compound (B) used in the flame-retardant resin composition of the present invention comprises a bromine compound represented by the above formula (1) as a main component and a bromine compound represented by the above formula (2). Is the same as the above-mentioned bromine compound in which the total amount is 0.02 mol or less per 1 mol of the bromine compound represented by the above general formula (1).

In the flame-retardant resin composition of the present invention, the inorganic flame-retardant auxiliary (C) used as required is one which increases flame retardancy by interaction with a bromine compound. There are, specifically, antimony trioxide, antimony pentoxide, boron trioxide, zinc borate, red phosphorus and the like, among which antimony trioxide and antimony pentoxide are particularly preferred.

The proportion of each component in the flame-retardant resin composition is 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight, and more preferably 1.5 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin. To 15 parts by weight, more preferably 2.5 to 1 part by weight.
0 parts by weight is more preferable, and 3 to 8 parts by weight is particularly preferable. If the amount is less than 1 part by weight, the flame-retardant effect is low, and 50
When the amount is more than the weight part, the thermal stability of the flame-retardant resin composition is lowered, and the mechanical properties are lowered.
Further, based on 100 parts by weight of the thermoplastic resin, the inorganic flame retardant is 0 to 25 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, .
Particularly preferred is 3 to 10 parts by weight. If the amount is more than 25 parts by weight, the mechanical properties deteriorate, which is not preferable.

The flame-retardant resin composition of the present invention is obtained by mixing these components in the above-mentioned mixing ratio, and using a Henschel mixer, a tumbler mixer, a super mixer, a Banbury mixer, a kneader, a roll, a single screw extruder, a twin screw extruder. It is manufactured by appropriately using a method of mixing and kneading with a machine or the like.

The flame-retardant resin composition of the present invention may contain a colorant, a pigment, a stabilizer, a plasticizer, a lubricant, an ultraviolet absorber, a filler, a reinforcing agent, a foaming agent, and other additives as required. Can be blended.

The flame-retardant resin composition obtained according to the present invention is extremely useful as a material for various applications including housings for home electric appliances and OA equipment, indoor and outdoor decorations, building materials, automobile parts and the like.

[0066]

Hereinafter, the present invention will be described in detail with reference to Examples.
Of course, it is not limited to this. The evaluation was performed according to the following methods (1) to (4).

(1) Purity of the bromine compound, content of the compound represented by the general formula (2) Purity of the bromine compound, represented by the general formula (2) described in the text corresponding to the starting compound used in the examples. The content of the compound to be measured was measured by high performance liquid chromatography (SCL-6B manufactured by Shimadzu Corporation) by a method of detecting the absorption at 280 nm. As for the purity of the bromine compound, the peak area ratio of the bromine compound to the sum of the peak areas of the respective components obtained from the chromatography was defined as 100. Further, in measuring the content of the compound represented by the general formula (2), the peak area of the bromine compound obtained by the chromatography is determined, and the peak area of the bromine compound is determined by the general formula (2).
Was determined, and the content (mol) of the main component relative to 1 mol of the bromine compound was calculated.

(2) Analysis of Moisture Content Coulometric titration moisture meter (CA-06 manufactured by Mitsubishi Chemical Corporation)
) And by the Karl Fischer method.

(3) Flame Retardancy The flame retardancy was evaluated using a 1/8 inch thick test piece according to the vertical combustion test method specified in UL-94 of UL standard.

(4) Thermal Stability The thermal stability was evaluated using an injection molding machine (SJ-25B manufactured by Meiki Seisakusho) at a molding temperature of 230 ° C. or 1 ° C.
Test pieces (length: 70 mm, width: 50 mm, thickness: 2 mm) were prepared, each of which was kept at 90 ° C. for 10 minutes, and its hue change (ΔE) was measured. According to JISZ-8730, the change of hue was measured using a color difference meter (SE-2000 manufactured by Nippon Denshoku Co., Ltd.).
The a and b values were measured and calculated by the following equation.

[0071]

(Equation 1)

Example 1 A glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat was recrystallized and purified from toluene with 99.8% purity.
300 g (0.48 mol) of 2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane and 511 g of methylene chloride dehydrated with a synthetic zeolite were added and dissolved. Further, 1.3 g (0.042 mol) of methanol, which was purified by distillation and then dehydrated by adding molecular sieve 4A, was added to this solution. The water content in this solution was 100 ppm.

Next, this solution was adjusted to 25 ° C., and 161.3 g (1.01 mol) of bromine was dropped from the dropping funnel over 30 minutes while stirring. At the end of the dropwise addition, the temperature of the reaction solution was 42 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, excess bromine in the reaction solution was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90 methylene chloride was separated from the methylene chloride layer.
%, And 1200 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
Dry under reduced pressure at 5 mmHg for 10 hours.
Bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane was obtained. This bromine compound has a purity of 98.3% and is represented by the general formula (2) based on 1 mol of 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane. The indicated compound having a phenolic hydroxyl group was 0.003 mol.

Example 2 A glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat was placed in a glass reactor having a purity of 99.5% of bis {(3,5-dibromo) purified by recrystallization with toluene. -4-allyloxy) phenyl}
311 g (0.48 mol) of sulfone and 511 g of methylene chloride dehydrated with synthetic zeolite were added and dissolved. Further, to this solution, ethanol 1.9 which was purified by distillation and then dehydrated by adding molecular sieve 4A was added.
g (0.042 mol) was added. The water content in this solution was 100 ppm.

Next, this solution was adjusted to 25 ° C., and 161.3 g (1.01 mol) of bromine was added dropwise from the dropping funnel over 30 minutes while stirring. At the end of the dropwise addition, the temperature of the reaction solution was 42 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, excess bromine in the reaction solution was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90 methylene chloride was separated from the methylene chloride layer.
%, And 1200 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
After drying under reduced pressure at 5 mmHg for 10 hours, bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone was mainly obtained. This bromine compound has a purity of 97.7% and is represented by the general formula (2) based on 1 mol of bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone. The compound having a phenolic hydroxyl group was 0.008 mol.

Example 3 A glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel, and a thermostat was charged with 98.6% pure bis {(3,5-dibromo) purified by recrystallization with toluene. -4-allyloxy) phenyl}
287 g (0.48 mol) of methane and 511 g of methylene chloride dehydrated with a synthetic zeolite were added and dissolved. Further, into this solution, 2.5 g (0.042 mol) of i-propanol, which was subjected to distillation and purification followed by addition of molecular sieve 4A and dehydration treatment, was added. The water content in this solution was 100 ppm.

Next, this solution was adjusted to 25 ° C., and 161.3 g (1.01 mol) of bromine was added dropwise from the dropping funnel over 30 minutes while stirring. At the end of the dropwise addition, the temperature of the reaction solution was 42 ° C. After the completion of the dropwise addition, the reaction solution was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, excess bromine in the reaction solution was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90 methylene chloride was separated from the methylene chloride layer.
%, And 1200 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
It was dried under reduced pressure at 5 mmHg for 10 hours to obtain mainly bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] methane. This bromine compound has a purity of 96.8% and bis [@ 3,5-dibromo-
4- (2,3-dibromopropyloxy) @phenyl]
The compound having a phenolic hydroxyl group represented by the general formula (2) was 0.018 mol with respect to 1 mol of methane.

Example 4 A glass reactor equipped with a stirrer, condenser, thermometer, dropping funnel and thermostat was recrystallized and purified with toluene at a purity of 99.5% (3,3 ′, 5,5). 280 g (0.48 mol) of 5'-tetrabromo-4,4'-diallyloxy) biphenyl and 511 g of methylene chloride dehydrated with synthetic zeolite
And dissolved. In addition, molecular sieve 4A was added to this solution after distillation and purification, and dehydration treatment was performed.
2.5 g (0.042 mol) of propanol were added. The water content in this solution was 100 ppm.

Next, this solution was cooled to 2 ° C., and 161.3 g (1.01 mol) of bromine was dropped from the dropping funnel over 30 minutes while stirring. At the end of the dropwise addition, the temperature of the reaction solution was 15 ° C. After the completion of the dropwise addition, the reaction solution is
The stirring was continued for another minute, and the addition reaction of bromine was completed.

Next, excess bromine in the reaction solution was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90 methylene chloride was separated from the methylene chloride layer.
%, And 1200 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
Dry under reduced pressure at 5 mmHg for 10 hours.
3 ', 5,5'-Tetrabromo-4,4'-di (2,3
-Dibromopropyloxy)] biphenyl was obtained. This bromine compound has a purity of 97.9% and [3, 3 ', 5,
The compound having a phenolic hydroxyl group represented by the general formula (2) was 0.007 mol per 1 mol of 5'-tetrabromo-4,4'-di (2,3-dibromopropyloxy)] biphenyl. .

Comparative Example 1 A glass reactor equipped with a stirrer, a condenser, a thermometer, a dropping funnel and an ice bath was charged with 97.2% pure 2,2-bis {(3,5-
Dibromo-4-allyloxy) phenyl @ propane 30
0 g (0.48 mol) and 511 g of methylene chloride were added and dissolved. The water content in this solution was 500 ppm.

Next, the solution was cooled to 2 ° C., and 161.3 g (1.01 mol) of bromine was added dropwise from the dropping funnel over 30 minutes with stirring. At the end of the dropwise addition, the temperature of the reaction solution was 15 ° C. After the completion of the dropwise addition, the reaction solution is
The stirring was continued for another minute, and the addition reaction of bromine was completed.

Next, excess bromine in the reaction solution was reduced with a 15% by weight aqueous sodium hydrogen sulfite solution, and the generated hydrogen bromide was neutralized with a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90 methylene chloride was separated from the methylene chloride layer.
%, And 1200 mL of methanol was added thereto to precipitate a reaction product. The precipitate was filtered to remove a massive solid. This massive solid is crushed in a mortar,
Dry under reduced pressure at 5 mmHg for 10 hours.
Bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane was obtained. This bromine compound has a purity of 91.7% and is represented by the general formula (2) based on 1 mol of 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane. The amount of the compound having a phenolic hydroxyl group shown was 0.041 mol.

[Example 5] High impact polystyrene resin [HIPS; Stylon 492 manufactured by Asahi Kasei Corporation]
R-H27-71], 6 parts of the bromine compound obtained in Example 1 and 0.6 part of antimony trioxide were added to 100 parts, and mixed with a tumbler-type blender, followed by a twin-screw extruder [Ikekai Iron Works Co., Ltd. ) PCM-30], pelletize at a cylinder temperature of 160 ° C, and then use an injection molding machine [Ltd.
A test piece (one that was not retained and one that was retained for 10 minutes) was molded at a molding temperature of 230 ° C by SJ-25B manufactured by Meiki Seisakusho Co., Ltd. Using the obtained test pieces, the flammability and heat stability were evaluated, and the results are shown in Table 1.

[Embodiment 6] In Embodiment 5, Embodiment 1
A test piece was molded in the same manner as in Example 5 except that the bromine compound obtained in Example 2 was used instead of the bromine compound obtained in the above, and the flammability and heat stability were evaluated. Are shown in Table 1.

[Embodiment 7] In Embodiment 5, Embodiment 1
A test piece was molded in the same manner as in Example 5 except that the bromine compound obtained in Example 3 was used instead of the bromine compound obtained in the above, and the flammability and heat stability were evaluated. Are shown in Table 1.

[Embodiment 8] In Embodiment 5, Embodiment 1
A test piece was molded in the same manner as in Example 5 except that the bromine compound obtained in Example 4 was used instead of the bromine compound obtained in Example 5, and the flammability and heat stability were evaluated. Are shown in Table 1.

[Embodiment 9] In Embodiment 5, Embodiment 1
A test piece was molded in the same manner as in Example 5 except that antimony trioxide was not used, except that 6 parts of the bromine compound obtained in the above was used as 10 parts, and the flammability and heat stability were evaluated. 1 is shown.

Example 10 In Example 5, instead of 0.6 parts of antimony trioxide, 1.0 part of antimony pentoxide was used.
A test piece was molded in the same manner as in Example 5 except that the part was used, and the flammability and heat stability were evaluated.
It was shown to.

Example 11 Polypropylene resin [P
P; K-1016 manufactured by Chisso Petrochemical Industries, Ltd.] 100
To the mixture, 8 parts of the bromine compound obtained in Example 1 and 4 parts of antimony trioxide were added, and mixed with a tumbler-type blender, followed by a twin-screw extruder [PCM-3 manufactured by Ikegai Iron Works Co., Ltd.]
0], and pelletized at a cylinder temperature of 160 ° C., and then a test piece (one that was not retained and one that was retained for 10 minutes) was molded at a molding temperature of 190 ° C. using an injection molding machine [SJ-25B manufactured by Meiki Seisakusho Co., Ltd.]. . Using the obtained test pieces, the flammability and heat stability were evaluated, and the results are shown in Table 1.

[Comparative example 2]
A test piece was molded in the same manner as in Example 5 except that the bromine compound obtained in Comparative Example 1 was used instead of the bromine compound obtained in the above, and the flammability and heat stability were evaluated. Are shown in Table 1.

[0095]

[Table 1]

The content (mole) of the compound represented by the general formula (2) represents the amount based on 1 mol of the obtained main component of the bromine compound.

[0097]

Industrial Applicability The bromine compound and the flame-retardant resin composition of the present invention have a small change in color tone upon melting, have a good appearance of molded articles, and have high flame-retardant performance. There is something special.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/43 C08K 5/43 C08L 23/00 C08L 23/00 25/00 25/00 101/00 101 / 00 F-term (reference) 4H006 AA03 AA05 AB99 GP02 GP03 GP11 GP12 GP20 GP21 GP22 4J002 BB031 BB051 BB061 BB071 BB081 BB121 BB141 BB151 BC031 BC041 BC061 FD091 FD061 FD061 FD071 GL00 GN00

Claims (9)

[Claims] 1. A composition comprising (B) 1 to 50 parts by weight of a bromine compound and (C) 0 to 25 parts by weight of an inorganic flame retardant, based on 100 parts by weight of a thermoplastic resin (A). ,
A bromine compound represented by the following general formula (1) as a main component,
The flame-retardant resin composition, wherein the content of the bromine compound represented by the following general formula (2) is 0.02 mol or less per 1 mol of the bromine compound represented by the following general formula (1). . Embedded image (Where X is a halogen atom, m and n are integers of 1 to 6, p and q are integers of 0 to 10 and p + q is 1 or more, and Ar ¹ and Ar ² may be the same or different. Often represents an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, or a ketone. Group,
It is a kind selected from an alkylene oxide group having 2 to 6 carbon atoms and a single bond, and R ¹ and R ² are a hydrocarbon group having 2 to 11 carbon atoms. ) (Where X, m, n, Ar ¹ , Ar ² , Y and R ¹ have the same meanings as defined in the general formula (1),
Is an integer of 1 to 10. ) 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polystyrene resin or a polyolefin resin. 3. The bromine compound (B) is represented by the general formula (1)
And a bromine compound represented by the following general formula (2)
Is in the range of 0.0001 to 0.001 mol per mol of the bromine compound represented by the general formula (1).
The flame-retardant resin composition according to claim 1, wherein the amount is 02 mol. 4. The method according to claim 1, wherein the bromine compound represented by the general formula (1) is 2,2-bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] propane, 2,2
-Bis [3,5-dibromo-4- (2,3-dibromo-
2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl] methane, [3,3 ', 5,5'-tetrabromo-4,4'-di (2,3-dibromopropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4, 4'-di (1,2-dibromoethyloxy)]
Biphenyl, bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] sulfone and bis [3,5-dibromo-4- (2,3-dibromo-2)
The flame-retardant resin composition according to claim 1, which is a compound selected from the group consisting of -methylpropyloxy) phenyl] sulfone. 5. The method according to claim 1, wherein the inorganic flame retardant is a thermoplastic resin.
The flame-retardant resin composition according to claim 1, wherein the amount is 0.1 to 20 parts by weight based on parts by weight. 6. An inorganic flame-retardant auxiliary agent comprising antimony trioxide,
The flame-retardant resin composition according to claim 1, which is at least one compound selected from the group consisting of antimony pentoxide, boron trioxide, zinc borate, and red phosphorus. 7. A bromine compound represented by the following general formula (1) comprising a bromine compound represented by the following general formula (1) as a main component and a bromine compound represented by the following general formula (1):
A bromine compound characterized by being at most 0.02 mol per mol. Embedded image (Where X is a halogen atom, m and n are integers of 1 to 6, p and q are integers of 0 to 10 and p + q is 1 or more, and Ar ¹ and Ar ² may be the same or different. Often represents an aromatic hydrocarbon group having 5 to 16 carbon atoms or a saturated alicyclic hydrocarbon group having 5 to 12 carbon atoms, and Y represents a saturated hydrocarbon group having 1 to 6 carbon atoms, a sulfone group, a sulfide group, or a ketone. Group,
It is a kind selected from an alkylene oxide group having 2 to 6 carbon atoms and a single bond, and R ¹ and R ² are a hydrocarbon group having 2 to 11 carbon atoms. ) (Where X, m, n, Ar ¹ , Ar ² , Y and R ¹ have the same meanings as defined in the general formula (1),
Is an integer of 1 to 10. ) 8. The bromine compound represented by the above general formula (1) has a content of the bromine compound represented by the above general formula (2) which is lower than that of the bromine compound 1 represented by the above general formula (1).
The bromine compound according to claim 7, wherein the amount is 0.0001 to 0.02 mol per mol. 9. The method according to claim 1, wherein the bromine compound represented by the general formula (1) is 2,2-bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] propane, 2,2
-Bis [3,5-dibromo-4- (2,3-dibromo-
2-methylpropyloxy) phenyl] propane, bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy)
Phenyl] methane, [3,3 ', 5,5'-tetrabromo-4,4'-di (2,3-dibromopropyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4, 4'-di (1,2-dibromoethyloxy)]
Biphenyl, bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] sulfone and bis [3,5-dibromo-4- (2,3-dibromo-2)
8. The bromine compound according to claim 7, which is a compound selected from the group consisting of -methylpropyloxy) phenyl] sulfone.