JP2569643B2 - Bis (biphenyl) diester derivative and method for producing the same - Google Patents

Description

The present invention relates to a novel bis (biphenyl) diester derivative and a method for producing the same.

(Prior Art) Conventionally, various types of halogen-containing flame retardants, phosphorus-containing flame retardants, phosphorus-containing halogen-containing flame retardants, inorganic compounds and the like have been known as flame retardants for synthetic polymers. However, many of these flame retardants generally have drawbacks in weather resistance and heat resistance.
In addition, when blended with a polymer, the polymer has reduced mechanical properties and electrical properties, and has reduced the intrinsic properties of the polymer, such as coloring of the polymer. In addition, there was a defect that the molding tank was corroded by the thermal decomposition of the flame retardant during polymer molding.

(Problems to be Solved by the Invention) With the recent development of highly heat-resistant polymers, the temperature at which the polymers are used has been increasing. In order to make these high heat resistant polymers flame retardant, a flame retardant that is thermally stable even at the temperature at which the polymer is used is required. Also, when considering using a polymer containing a flame retardant outdoors,
A flame retardant with good weather resistance is required. Therefore, an object of the present invention is to provide a flame retardant having high heat resistance and high weather resistance.

(Means for Solving the Problems) In view of the above circumstances, the present inventor has synthesized various compounds and, as a result of intensive studies on a novel compound that can be suitably used as a flame retardant having high heat resistance and high light resistance, has been identified. It has been found that the halogen-containing compound of the present invention satisfies such a condition, and the present invention has been achieved.

That is, the present invention relates to the general formula (1) (Wherein X represents bromine or chlorine, m = 0 to 9, n = 0 to 9)
, M + n> 1, and R is an alkylene group having 1 to 4 carbon atoms, and a hydrogen atom contained in these groups may be substituted with a halogen atom. A bis (biphenyl) diester derivative represented by general formula (2) (Wherein X represents bromine or chlorine and represents a number of m = 0 to 9) and a phenylphenol compound represented by the general formula (3) ClCO-R-COCl (3) (where R represents a carbon atom having 1 to 4 carbon atoms). An alkylene group or a phenylene group, wherein a hydrogen atom contained in these groups may be substituted with a halogen atom.) And a process for producing the bis (biphenyl) diester derivative represented by the formula:

The bis (biphenyl) diester derivative represented by the general formula (1) of the present invention is a novel compound and has at least one halogen atom in the molecule. As the halogen, bromine and chlorine are preferred.

Specific examples of the compound represented by the general formula (1) of the present invention include bis (octabromobiphenyl) succinate, bis (octabromobiphenyl) fumarate, bis (octabromobiphenyl) adiporate, bis (hexabromobiphenyl) succinate , Bis (hexabromobiphenyl) fumarate, bis (hexabromobiphenyl) adipate, bis (octachlorobiphenyl)
Succinate, bis (octachlorobiphenyl) fumarate, bis (octachlorobiphenyl) adipate,
Bis (hexachlorobiphenyl) succinate, bis (hexachlorobiphenyl) fumarate, bis (hexachlorobiphenyl) adipate, bis (octabromobiphenyl) -2,3-dibromosuccinate, bis (hexabromobiphenyl) -2,3-dichlorosuccinate , Bis (octachlorobiphenyl) -2,3-dibromosuccinate, bis (hexachlorobiphenyl) -2,3
-Dichlorosuccinate and the like.

Next, the method for producing the bis (biphenyl) diester derivative of the present invention will be specifically described. Examples of the production method include a method of reacting a phenylphenol compound with a dicarboxylic acid dichloride compound.

General formula (2) (Wherein X represents bromine or chlorine and m represents a number from 0 to 9), such as tribromophenylphenol, hexabromophenylphenol, octabromophenylphenol, trichlorophenylphenol, Hexachlorophenylphenol, octachlorophenylphenol, etc. and the general formula (3) ClCO-R-COCl (3) (R is an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom contained in these groups is a halogen atom. A dicarboxylic acid dichloride compound represented by the following formula: phthalyl dichloride, isophthalyl dichloride,
Terephthalyl dichloride, oxalyl dichloride, malonyl dichloride, succinyl dichloride, glutaryl dichloride, adipoyl dichloride, 3,4-dibromophthalyl dichloride, 3,4-dibromoisophthalyl dichloride, 2,3,5,6-tetrabrad Moterephthalyl dichloride,
2,3-dibromomalonyl dichloride, 3,4-dibromosuccinyl dichloride, 3,4-dichlorophthalyl dichloride, 3,4-dichloroisophthalyl dichloride, 2,3,5,6-
Reacting tetrabramoterephthalyl dichloride, 2,3-dichloromalonyl dichloride, 3,4-dichlorosuccinyl dichloride, etc. to obtain a compound of the general formula (1) (Wherein X represents bromine or chlorine, m = 0 to 9, n = 0 to 9)
, M + n> 1, and R is an alkylene group or a phenylene group having 1 to 4 carbon atoms, and a hydrogen atom contained in these groups may be substituted with a halogen atom. ) Is obtained.

The ratio of the phenylphenol compound at the time of the reaction is 2 times or more, preferably 2 to 2.5 times, the mole of the dicarboxylic acid dichloride compound.

The reaction is preferably performed in a solvent dried by an arbitrary method, and a solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzene, toluene, xylene, ethylbenzene, or the like may be used alone or in combination.

Further, it is preferable to add a base represented by amines, for example, triethylamine, tetramethylurea, dimethylaniline, pyridine and the like to the reaction system in an equimolar amount or more, preferably 1 to 1.5 times, with respect to the phenylphenol compound.

The reaction may be carried out at a temperature ranging from 0 ° C to the boiling point of the solvent, preferably from room temperature to 70 ° C. The reaction time is also appropriately selected depending on other conditions and is not particularly limited, but may be 30 minutes or more, preferably 1 hour or more.

(Effect) The novel compound bis (biphenyl) diester derivative of the present invention is useful as a polymer flame retardant having a high melting point and excellent weatherability and heat resistance.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these.

Example 1 [1] Synthesis of octabromophenylphenol In a 5 l flat-bottomed four-necked separable flask equipped with a cooling condenser with a hydrogen bromide trap and a power stirrer, phenylphenol (500 g) and chloroform (3.
0l) and heated to 40 ° C on a stirring oil bath. To this, 2.3 l of bromine was added dropwise to obtain a chloroform bromine solution containing phenylphenol low bromide.

Chloroform (2.0 l), iron powder (32.8 g) and iodine (3.0 g) are placed in a 5 l flat four-necked separable flask equipped with a cooling condenser with a hydrogen bromide trap and a power stirrer, and the oil bath is stirred. The mixture was refluxed under chloroform (63 ° C.) and stirred for 30 minutes. A chloroform-bromine solution containing phenylphenol and low bromide, which had been synthesized in advance, was added dropwise thereto over 6 hours. After cooling, the reaction solution was added dropwise to a hydrochloric acid aqueous solution at 70 ° C. to precipitate a solid, and at the same time, chloroform and bromine were distilled off. After cooling, the mixture was filtered, and a saturated aqueous solution of sodium hydrogen sulfite (1.0 L),
Washing with water (5.0 l) and successive drying and drying (200 ° C. for 2 hours) gave a pale yellow solid. Yield 2368.9 g. The elemental analysis values were as follows: C: 17.9%, H: 0.4%, Br: 80.0%, (calculated value: C:
(17.99%, H: 0.25%, Br: 79.77%). In addition, analysis by high-performance gel permeation chromatography using a column (eluent: tetrahydrofuran) of TSK GEL G-1000H (Tosoh Corporation) confirmed that the product was pure. From the above, it was confirmed that a compound in which X in the general formula (2) was Br and m = 8 was synthesized.

The thermal stability of the compound obtained above was analyzed by TGA under the following conditions, and the results are shown in Table 1.

Gas Air Gas Flow 30.50ml / min Rate 10 ℃ / min Temp rt ~ 500 ℃ [2] Synthesis of bis (octabromobiphenyl) succinate In a 5 l flat bottom four-necked separable flask equipped with a calcium chloride tube and a power stirrer, octabromophenyl phenol (250.0 g), benzene (2.5 l), triethylamine (31.6 g) ) Was added sequentially and stirred to obtain a homogeneous solution. To this, succinyl dichloride (24.2 g) in benzene (0.2 l) solution was added dropwise over 2 hours using a dropping funnel, followed by aging for 1 hour. Thereafter, the mixture was filtered, washed with benzene (1.0 L) and i-propanol (1.0 L), and dried (120 L).
C. for 8 hours) to obtain white crystals. Yield 232.
It was 12 g. The elemental analysis values are C: 19.8%, H: 0.4%, B
r: 75.9%, (calculated values C: 19.96%, H: 0.36%, Br: 75.88
%). In addition, analysis by high-performance gel permeation chromatography using a column (eluent: tetrahydrofuran) of TSK GEL G-1000H (Tosoh Corporation) confirmed that the product was pure. The Looking measuring the IR spectra of the obtained compound, ester C = O stretching vibration of the disappeared stretching vibration of O-H of 3200~3600cm ^-1 1755cm ^-1 is newly generated. From the above, X = Br in the general formula (1),
It was confirmed that a compound of m = n = 8 and R = CH ₂ CH ₂ was synthesized.

The thermal stability of the compound obtained above was analyzed by TGA under the same conditions as described above, and the results are shown in Table 2.

Example 2 Octabromophenylphenol (250.0 g), benzene (2.5 l), and triethylamine (31.6 g) were sequentially added to a 5 l flat bottom four-necked separable flask equipped with a calcium chloride tube and a power stirrer, and stirred. This gave a homogeneous solution. Terephthalyl dichloride (31.0 g) in a benzene (1.0 l) solution was added dropwise over 2 hours using a dropping funnel, and the mixture was aged for 1 hour after the addition. Thereafter, filtration, washing with benzene (1.0 L) and i-propanol (1.0 L) and drying (200 ° C. for 2 hours) gave white crystals. The yield was 270.0 g. The elemental analysis values were C: 22.0% and H: 0.
4, Br: 73.9%, (calculated C: 22.18%, H 0.35%, Br: 73.78
%). In addition, analysis by high-performance gel permeation chromatography using a column (eluent: tetrahydrofuran) of TSK GEL G-1000H (Tosoh Corporation) confirmed that the product was pure. The Looking measuring the IR spectra of the obtained compound, disappeared stretching vibration of O-H of 3200～3600Cm ^-1, ester C = O stretching vibration of 1750 cm ^-1 is newly generated. From the above, X in the general formula (1) is Br
It was confirmed that the compound of m = n = 8 and R = C ₆ H ₄ was synthesized.

The thermal stability of the compound obtained above was analyzed by TGA under the same conditions as described above, and the results are shown in Table 3.

Claims (2)

(57) [Claims] 1. The general formula (1) (Wherein X represents bromine or chlorine, m = 0 to 9, n = 0 to 9)
, M + n> 1, and R is an alkylene group having 1 to 4 carbon atoms, and a hydrogen atom contained in these groups may be substituted with a halogen atom. A) bis (biphenyl) diester derivative represented by the formula: 2. The general formula (2) (Wherein X represents bromine or chlorine and represents a number of m = 0 to 9) and a general formula (3) ClCO-R-COCl (R is an alkylene group having 1 to 4 carbon atoms) Wherein the hydrogen atom contained in these groups may be replaced by a halogen atom.), And reacting with a dicarboxylic acid dichloride compound represented by the formula (1): A method for producing a (biphenyl) diester derivative. (Wherein X represents bromine or chlorine, m = 0 to 9, n = 0 to 9)
, M + n> 1, and R is an alkylene group having 1 to 4 carbon atoms, and a hydrogen atom contained in these groups may be substituted with a halogen atom. A) bis (biphenyl) diester derivative represented by the formula: