JP2000086563A - Bromine compound and flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bromine compound not causing its volatilization and bleedout substantially when heat-processing and in final molded products and having excellent flame retardant effect, and to provide an olefin-based flame retardant resin compound including the same. SOLUTION: This bromine compound comprises 2,2-bis[3,5-dibromo-4-(2,3- dibromopropyloxy)phenyl]propane as a main ingredient and has 0.01-0.1 ratio (B/A) of heat of fusion when measured with DSC, in which A (J/g) is the heat of fusion of 2,2-bis[3,5-dibromo-4-(2,3-dibromopropyloxy)phenyl]propane at the melting point X deg.C and B (J/g) is the heat of fusion of other compounds having the melting point ranging from (X-60) deg.C to (X-20) deg.C at their melting point. This flame retardant resin composition comprises 100 pts.wt. olefin-based resin, 1-50 pts.wt. bromine compound mentioned above and 0-25 pts.wt. inorganic auxiliary for a flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bromine compound and a flame-retardant resin composition, and more particularly, a bromine compound having a low bleed-out and exhibiting a high flame-retardant effect as a flame retardant for a polyolefin resin. And a flame-retardant resin composition containing the same.

[0002]

2. Description of the Related Art Heretofore, as a method for flame retarding polyolefin resins, a method in which a bromine compound and an antimony compound are added in combination has been widely used in practice because of its excellent flame retarding effect. Among these bromine compounds, it is known that (2,3-dibromopropyl) ether of brominated bisphenol A has a relatively high flame retardant effect as compared with other flame retardants.
However, in order to comply with a high flame retardant standard, this compound requires a large amount of addition to a polyolefin-based resin, which may cause bleed-out and cause a problem such as a defective surface of a molded product.

As a method for making a polyolefin resin flame-retardant, the addition of a phosphorus compound such as a phosphoric acid ester, a phosphite or a red phosphorus has been proposed, but it is more difficult than a method of adding a bromine compound. Not only is the combustion effect small,
It has very poor compatibility with polyolefin resins and is hardly used. In recent years, in order to improve such disadvantages,
Various modifications of phosphorus compounds have been proposed, but none of them have substantially no bleed-out and have an excellent flame-retardant effect. Further, the addition of the phosphorus compound may significantly reduce the physical properties of the resin.

For example, Japanese Patent No. 2588331 proposes a method of adding a phosphoric acid-based flame retardant supported on an inorganic powder to a polyolefin-based resin.
However, this method has a problem that the usable applications are considerably limited due to drawbacks such as a decrease in mechanical properties of the obtained resin and insufficient heat resistance due to a decrease in the weight deflection temperature.

[0005]

SUMMARY OF THE INVENTION The present inventors have developed a bromine compound which has substantially no volatilization and bleed-out of a bromine compound at the time of heat processing or in a final molded product and which has an excellent flame-retardant effect. As a result of intensive studies aimed at providing a blended polyolefin-based flame-retardant resin composition, we focused on the heat of fusion of a specific bromine compound in DSC. By adjusting the heat ratio to a specific range, it has been found that the compatibility with the polyolefin resin can be improved and the bleed out can be prevented while maintaining the flame retardant effect, and the present invention has been achieved.

[0006]

That is, according to the present invention, 2,2-bis [3,5-dibromo-4- (2,3-
A bromine compound containing dibromopropyloxy) phenyl] propane as a main component, wherein the bromine compound is (A) 2,2-bis [3,5-dibromo-
Of 4- (2,3-dibromopropyloxy) phenyl] propane at the melting point (X [deg.] C.). DELTA.A (J /
g)｝ and (B) due to other compounds (X-60) ~
(X-20) heat of fusion at the melting point in the range of (° C) ℃ B (J
/ G)} (heat of fusion; B / A) of 0.01 to 0.1.
1 is provided.

Further, according to the present invention, (I) 1 to 50 parts by weight of a bromine compound and (III) 0 to 2 parts of an inorganic flame retardant per 100 parts by weight of a polyolefin resin.
5 parts by weight, and the bromine compound is a bromine compound containing 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane as a main component. The compound was measured by DSC,
(A) 2,2-bis [3,5-dibromo-4- (2,3
[Dibromopropyloxy) phenyl] propane at the melting point (X ° C) {A (J / g)} and (B) the range of (X-60) to (X-20) ° C due to other compounds. A ratio of heat of fusion {B (J / g)} at the melting point of (B / A) of 0.01 to 0.1 is provided. You.

The bromine compound of the present invention comprises 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane (hereinafter sometimes abbreviated as TBA-BE). TBA-BE as the main component
Besides the melting point (X ° C.) of TBA-BE (X-6
0) to (X-20) a small proportion of a compound having a melting point in the range of ° C. TBA which is the main component of this bromine compound
-BE has a melting point (XC) in the range of 105 to 120C as measured by DSC.

[0009] Further, as the compound contained in such a small proportion, specifically, 2- [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] -2-
[3'-bromo-4 '-(2,3-dibromopropyloxy) phenyl] propane, 2- [3,5-dibromo-
4- (2,3-dibromopropyloxy) phenyl]-
2- [3 ', 5'-dibromo-4'-(2-hydroxy-3-bromopropyloxy) phenyl] propane, 2
-[3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] -2- [3 ', 5'-dibromo-
4 '-(2-bromo-3-hydroxypropyloxy)
Phenyl] propane, 2- [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] -2-
[3 ', 5'-dibromo-4'-(hydroxy) phenyl] propane and the like. These compounds usually exhibit a melting point of 50 to 90 ° C.

In the present invention, (A) TBA-B
The heat of fusion {A (J / g)} at the melting point (X ° C.) of E and the compound contained in a small proportion of (B) (X-6)
0) to a ratio (B / A) of 0.0 to the heat of fusion (B (J / g)) at the melting point in the range of (X-20) ° C.
It is important that it be 1 to 0.1. When the proportion of the low melting point compound as the component (B) satisfies the above range of the heat of fusion, the compatibility between the bromine compound and the polyolefin resin can be improved, and bleed out can be prevented. When the heat of fusion (B / A) is less than 0.01, it is difficult to suppress the bleed out of the bromine compound from the polyolefin-based resin composition. It is not preferable because the heat resistance of the resin composition decreases.

In the present invention, the melting point is determined by using a differential scanning calorimeter (DSC)
This is the temperature of the peak value of the curve, which is obtained by reading the temperature.

[0012] The heat of fusion referred to in the present invention means the amount of heat absorbed by melting, which is measured using a differential scanning calorimeter (DSC) and determined from the peak area. Specifically, the DS of a sample measured at a temperature rising rate of 10 to 40 ° C./min in an atmosphere of an inert gas such as nitrogen or argon is used.
The peak area of the C-curve is determined, and the peak area of indium measured under the same apparatus and under the same conditions is corrected by a value determined using a known heat of fusion.

The method for producing the bromine compound of the present invention includes, for example, (1) 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (hereinafter abbreviated as TBA) having a purity of about 95 to 99%. 1.9 to 2.5 mol of allyl chloride per 1 mol of an aqueous alkali solution and 1 carbon atom
And 2,2-bis [3,5-dibromo-4- (allyloxy) phenyl] having a purity of about 90 to 97%.
A solution in which propane (hereinafter, abbreviated as TBA-AE) is collected by filtration, and a solution obtained by dissolving the TBA-AE in a solvent such as methylene chloride without drying the wet solid without drying;
A method of mixing and reacting with bromine or a bromine solution to cause bromination, or (2) 1 to 10 mol, preferably 1.2 to 10 mol of allyl halide such as allyl chloride to 1 mol of TBA having a purity of about 95 to 99%. 5 mol, more preferably 1.5 to 3 mol, particularly preferably 1.9 to 2.5 mol is a solvent which is incompatible with an aqueous alkali solution and water and which is inert to allyl halides such as allyl chloride (for example, xylene In the presence of 4)
The reaction was carried out at 0 to 110 ° C., and after the reaction was completed, the aqueous layer was separated.
A method in which the obtained organic layer in which TBA-AE having a purity of 90 to 97% is dissolved, and bromine or a bromine solution are mixed, reacted, and brominated can be employed.

In the above method (1), the solvent inert to the reaction used to dissolve TBA-AE is TBTB.
The higher the solubility in A-AE, the better, but it may be in a partially dissolved state. That is, any compound may be used as long as the bromine compound generated by the bromination reaction of TBA-AE can 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. Among them, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, and acetone chloride, and aromatic hydrocarbon compounds such as benzene, toluene, and xylene. Preferably, methylene chloride, chloroform, toluene and xylene are more preferable, and methylene chloride is particularly preferably used. These solvents are used alone or in combination of two or more.

Further, as the solvent which is incompatible with water used in the method (2) for producing TBA-AE and which is inactive against allyl halide such as allyl chloride, methylene chloride,
Halogen-containing hydrocarbon compounds such as chloroform, 1,2-dichloroethane, 1,1-dichloroethane, bromoethane, butyl chloride, chloropropane, chlorobenzene, and acetone chloride, and aromatics such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, and isopropylbenzene. Examples thereof include hydrocarbons, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene. Toluene and xylene are preferably used, and xylene is particularly preferably used. These solvents are used alone or in combination of two or more.

Further, 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 of mixing a solution in which BA-AE is dissolved in a solvent and bromine or a bromine solution, bromine or a bromine solution is mixed with T
Method of adding to and mixing with a solution of BA-AE, TBA-A
E solution may be added to bromine or a bromine solution and mixed, or bromine or a bromine solution and a TBA-AE solution may be simultaneously added to a 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 pressure or under 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 such a bromine compound, a so-called batch method may be employed, in which a fixed amount is added to the reaction tank to terminate the bromination reaction, or the bromination reaction can be carried out continuously. While a raw material is continuously introduced, a take-out port is provided in a part of the reaction tank to draw out a part of the reaction solution, and the reaction solution can be 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 is determined by adding TB to obtain a desired bromine compound.
A sufficient molar ratio to A-AE is sufficient.
The amount of bromine is preferably from 2 to 20 mol, more preferably from 2 to 10 mol, and more preferably from 2 to 10 mol, based on 1 mol of BA-AE.
A range of 6 mol is more preferable, and a range of 2 to 3.5 mol is particularly preferable.

The desired bromine compound can be separated and recovered from the reaction mixture obtained by the above-mentioned bromination reaction by a method known per se. However, unreacted bromine remains in the reaction mixture. Therefore, the method of treating residual bromine with a reducing agent, converting bromine into hydrobromic acid once, and then adding an alkaline neutralizing agent is usually used. Has been adopted.

As the reducing agent used in such a treatment,
It is a reducing agent used in a normal reduction reaction, specifically, sodium bisulfite, sodium dithionite,
Sodium sulfite, oxalic acid, hydrogen sulfide, sodium nitrite, potassium nitrite, hydroxylamine sulfate, tin, stannous oxide, hydrazine, and the like; sodium bisulfite, sodium dithionite, sodium sulfite, oxalic acid, Sodium nitrate is preferably used. These reducing agents can also be used as an aqueous solution. These reducing agents are used alone or in combination of two or more.

Examples of the alkaline neutralizing agent include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates. ,Sodium hydroxide,
Potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, calcium carbonate, and the like are preferable, and sodium hydroxide is particularly preferably used. These alkaline neutralizing agents are preferably used as an aqueous solution. These alkaline neutralizing agents are used alone or in combination of two or more.

From the reaction mixture treated in the manner described above,
The desired bromine compound can be produced by a method known per se, for example, a lower alcohol having 1 to 6 carbon atoms, specifically methanol,
It is recovered by means such as precipitation with a poor solvent such as ethanol.

The bromine compound of the present invention is useful as a stabilizer for γ-ray resistance and a flame retardant. In particular, the compound containing the bromine compound of the present invention as a flame retardant in a polyolefin resin is The resin composition has improved compatibility and suppressed bleed-out.

The polyolefin resin (I) used in the flame-retardant resin composition of the present invention includes a homopolymer or a copolymer of olefins such as ethylene, propylene and butene, or a copolymerizable with these olefins. It is a copolymer with the components, specifically, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-
Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer, propylene-butene copolymer and the like. Among them, polypropylene is preferably used. These can be used alone or in combination of two or more, and if desired, other resins may be blended as a small component.

The (II) bromine compound used in the flame-retardant resin composition of the present invention is 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane. A bromine compound as a main component, wherein the bromine compound is obtained by measuring (A) 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane by DSC. Heat of fusion {A (J / g)} at the melting point (X ° C) and heat of fusion at the melting point in the range (X-60) to (X-20) ° C due to the other compound (B) ｛B ( (J / g)} (the heat of fusion; B / A) is 0.01 to 0.1.

In the flame-retardant resin composition of the present invention, as the (III) inorganic flame-retardant auxiliary used as required, the flame retardancy is increased 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 based on 100 parts by weight of the polyolefin resin.
The bromine compound is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight. If the amount is less than 1 part by weight, the flame-retardant effect is low, and if it is more than 50 parts by weight, the thermal stability of the flame-retardant resin composition is reduced, and the mechanical properties are undesirably reduced. 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, .3-10
Part by weight is particularly preferred. If the amount is more than 25 parts by weight, the mechanical properties of the flame-retardant resin composition decrease, which is not preferable.

The flame-retardant resin composition of the present invention is prepared by blending 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.

When the flame-retardant resin composition of the present invention is used as a foam, a thermally decomposable foaming agent such as azodicarbonamide is added, and crosslinking is carried out in the presence of an organic peroxide. After irradiation crosslinking by radiation, it is desirable to foam by heating. Further, the resin composition of the present invention may optionally contain a coloring agent, a pigment, a stabilizer, a plasticizer, a lubricant, an ultraviolet absorber, a filler, a reinforcing agent, and other additives.

The flame-retardant resin composition obtained according to the present invention is extremely useful as a material for building materials, electric device materials, interior goods, and other miscellaneous goods.

[0034]

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) Measurement of Melting Point and Heat of Melting A DSC curve of a sample measured by a DuPont 2000 type DSC measuring apparatus under a nitrogen flow of 48 ml / min under a temperature rising condition of 20 ° C./min was obtained. The temperature of the peak value of the DSC curve was taken as the melting point, and the peak area was determined.
Using the peak area of indium measured under the same conditions and the known heat of fusion of 28.42 J / g, the heat of fusion at the melting point of the sample was determined.

(2) 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 the UL standard.

(3) Evaluation of Bleeding A molded plate (width 45 × length 70 × thickness 2 mm) was allowed to stand in an oven at 80 ° C. for 5 days and evaluated for the occurrence of bleed on the molded plate. The evaluation criterion was indicated by ○ when almost no bleeding was observed, and by X when the bleeding was almost observed.

(4) Purity of bromine compound The purity of the bromine compound was determined by high-performance liquid chromatography (SCL-6B manufactured by Shimadzu Corporation) by detecting the absorption at 280 nm, and obtained by this chromatography. The sum of the peak areas of each component was set to 100, and the peak area ratio of the target bromine compound to this was determined.

Example 1 484 g of water and 2,2-bis [(3,5-dibromo-4-hydroxyxy) were placed in a glass reactor equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat. ) Phenyl] propane (hereinafter referred to as T
436 g (0.8 mol) of NaOH7
0.4 g (1.76 mol) was added and dissolved. Then
192 g (242 ml) of methanol was charged. And
While maintaining the above solution at 55 ° C. and stirring at 500 rpm, 140.8 g (1.84 mol) of allyl chloride was added dropwise over 1 hour, and the reaction was carried out for 5 hours including the time required for the dropwise addition. The product was collected by filtration by centrifugation. The resulting precipitate was 2,2-bis [(3,5-dibromo-4-allyloxy) phenyl] propane (hereinafter, referred to as
TBA-AE), and its purity is 95.8.
%Met.

Subsequently, the wet solid 3 of TBA-AE obtained by the above method was placed in a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and an ice bath.
32 g (300 g of TBA-AE; 0.48 mol) and 511 g of methylene chloride were added and dissolved. The solution was then cooled to 2 ° C. and, with stirring, 161.3 g of bromine
(1.01 mol) was dropped from the dropping funnel over 30 minutes. 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 was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, the excess bromine in the reaction solution was reduced with 120 g of a 15% by weight aqueous solution of sodium bisulfite.
The produced hydrogen bromide was neutralized using a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution, and about 90% of the methylene chloride was evaporated and removed from the methylene chloride layer.
L was added to precipitate a reaction product, and the precipitate was filtered to remove a massive solid. This lumpy solid is crushed in a mortar,
After drying under reduced pressure at 5 mmHg at 80 ° C. for 10 hours, 2,2-bis [3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl] propane (hereinafter TB)
A-BE).

This bromine compound has a purity of 86.5%,
The heat of fusion of the first peak detected at 73 ° C. by DSC was 1.9 J / g, and the heat of fusion of the second peak detected at 115 ° C. was 28.3 J / g. The value divided by the heat of fusion of the second peak was 0.07.

Example 2 A glass reactor equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat was charged with 484 g of water, 436 g (0.8 mol) of TBA, N
70.4 g (1.76 mol) of aOH was added and dissolved.
Next, 406 g (472 ml) of xylene was added. Then, the above solution was kept at 40 ° C., and the rotation speed was 3000 rpm.
After stirring, 140.8 g (1.84 mol) of allyl chloride was added, and the temperature was raised to 80 ° C. The reaction was carried out for 5 hours including the time required for the temperature rise (75 minutes). After completion of the reaction, the aqueous layer was separated to obtain a xylene solution of TBA-AE. The purity of the TBA-AE in the bromine compound in the obtained solution was 97.
1%.

Subsequently, 55% by weight of TBA-AE obtained by the above method was placed in a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and an ice bath.
545 g of xylene solution (300 g of TBA-AE: 0.
48 mol). The solution is then cooled to 20 ° C. and, with stirring, 161.3 g (1.01 mol) of bromine
Was dropped from the dropping funnel over 30 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 25 ° 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 120 g of a 15% by weight aqueous sodium bisulfite solution.
The produced hydrogen bromide was neutralized using a 25% by weight aqueous sodium hydroxide solution. Thereafter, a xylene layer was separated from this solution, and 1200 ml of methanol was added to the xylene layer.
Was added to precipitate a reaction product, and 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 at 0 ° C.
BA-BE was obtained.

This bromine compound has a purity of 92.4%.
The heat of fusion of the first peak detected at 76 ° C. by DSC was 0.8 J / g, and the heat of fusion of the second peak detected at 113 ° C. was 33.4 J / g. The value divided by the heat of fusion of the second peak was 0.02.

Comparative Example 1 In a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat, 484 g of water, 436 g (0.8 mol) of TBA, N
70.4 g (1.76 mol) of aOH was added and dissolved.
Then, 192 g (242 ml) of methanol was added.
Then, the above solution was kept at 55 ° C., and the rotation speed was 500 rpm.
Under stirring, 140.8 g (1.84 mol) of allyl chloride was added dropwise over 1 hour, the reaction was allowed to proceed for 5 hours including the time required for the addition, and the precipitated reaction product was collected by filtration by centrifugation. . The collected precipitate is put in a glass container equipped with a stirrer, 300 g of water is added thereto, and the mixture is washed by stirring. Then, the collected precipitate is collected by filtration by centrifugal separation. Put, methanol 300
g was added and washed with stirring, and then collected by filtration by centrifugation. The collected material is kept at 80 ° C. for 10 hours at 5 mmHg.
And dried under reduced pressure to obtain TBA-AE. Its purity is 9
9.2%.

Subsequently, 300 g of the TBA-AE obtained by the above method was placed in a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and an ice bath.
(0.48 mol) and 511 g of methylene chloride dehydrated with synthetic zeolite were added and dissolved. The solution was then cooled to 2 ° C. and, with stirring, 161.3 g of bromine
(1.01 mol) was dropped from the dropping funnel over 30 minutes. 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 was continuously stirred for 30 minutes to terminate the bromine addition reaction.

Next, after reducing excess bromine in the reaction solution with 120 g of a 15% by weight aqueous solution of sodium bisulfite,
The produced hydrogen bromide was neutralized using a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from this solution. Subsequently, 300 g of this methylene chloride layer
Was placed in a glass flask equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a thermostat. At a temperature of 25 ° C., under stirring, 160 g of methanol was added to this solution at 4 g /
Minutes of addition. After completion of the dropwise addition of methanol, stirring was further continued at the same temperature for 30 minutes. TBA-B precipitated
E was filtered out and taken out at 80 ° C. for 10 hours at 5 mmHg.
And dried under reduced pressure to obtain mainly TBA-BE. This bromine compound has a purity of 97.8% and is measured by DSC.
One peak was detected at 108 ° C., and the heat of fusion of this peak was 42.0 J / g.

Example 3 Polypropylene resin [PP;
8 parts of the bromine compound obtained in Example 1 and 4 parts of antimony trioxide were added to 100 parts of K-1016 (manufactured by Chisso Petrochemical Industries, Ltd.) and mixed with a tumbler-type blender, followed by a twin-screw extruder [ Ikegai Iron Works Co., Ltd. PCM-30]
Then, a test piece was formed 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, flame retardancy and bleeding property were evaluated. The results are shown in Table 1.

[Embodiment 4] In Embodiment 3, Embodiment 1
A test piece was molded in the same manner as in Example 3 except that the bromine compound obtained in Example 2 was used instead of the bromine compound obtained in the above, and the flame retardancy and bleeding property were evaluated. Are shown in Table 1.

[Embodiment 5] In Embodiment 3, Embodiment 1
A test piece was molded in the same manner as in Example 3 except that antimony trioxide was not used except that 8 parts of the bromine compound obtained in the above was used as 15 parts, and the flame retardancy and bleeding property were evaluated. 1 is shown.

Example 6 A test piece was molded in the same manner as in Example 3 except that 8 parts of antimony pentoxide was used instead of 4 parts of antimony trioxide. The bleeding property was evaluated, and the results are shown in Table 1.

[Comparative example 2]
A test piece was molded in the same manner as in Example 3 except that the bromine compound obtained in Comparative Example 1 was used in place of the bromine compound obtained in Example 1, and the flame retardancy and bleeding property were evaluated. Are shown in Table 1.

[0055]

[Table 1]

[0056]

The bromine compound obtained by the present invention is suitably used as a flame retardant for a polyolefin resin, and since this flame retardant resin composition has little bleed-out and has high flame retardancy, Its industrial effects are exceptional.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA03 AB80 AC30 BB11 BB12 BC10 BC31 BC35 BE02 BE03 BE27 BE53 BM73 EA22 FE76 4J002 BB031 BB041 BB061 BB071 BB121 BB141 BB151 BB171 DA057 DE127 FD007 EJ056

Claims (4)

[Claims] 1. A composition comprising (II) 1 to 50 parts by weight of a bromine compound and (III) 0 to 25 parts by weight of an inorganic flame retardant, based on 100 parts by weight of a polyolefin resin. , 2,2-bis [3,5-dibromo-4-
A bromine compound containing (2,3-dibromopropyloxy) phenyl] propane as a main component, and the bromine compound is (A) 2,2-bis [3,5
-Dibromo-4- (2,3-dibromopropyloxy)
[Phenyl] propane's heat of fusion at the melting point (X ° C) {A (J / g)} and (B)
The ratio of heat of fusion (B / A) to the heat of fusion {B (J / g)} at the melting point in the range of 60) to (X-20) ° C is 0.0.
A flame-retardant resin composition, which is 1 to 0.1. 2. The flame-retardant resin composition according to claim 1, wherein the amount of the inorganic flame-retardant aid is 0.1 to 20 parts by weight based on 100 parts by weight of the polyolefin resin. 3. 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. 4. A 2,2-bis [3,5-dibromo-4- compound.
A bromine compound containing (2,3-dibromopropyloxy) phenyl] propane as a main component, and the bromine compound is (A) 2,2-bis [3,5
-Dibromo-4- (2,3-dibromopropyloxy)
[Phenyl] propane's heat of fusion at the melting point (X ° C) {A (J / g)} and (B)
The ratio of heat of fusion (B / A) to the heat of fusion {B (J / g)} at the melting point in the range of 60) to (X-20) ° C is 0.0.
A bromine compound having a ratio of 1 to 0.1.