WO2011078432A1

WO2011078432A1 - Preparation method of brominated diphenylethane mixture

Info

Publication number: WO2011078432A1
Application number: PCT/KR2009/008022
Authority: WO
Inventors: 안성희; 정진평
Original assignee: 제일모직주식회사
Priority date: 2009-12-24
Filing date: 2009-12-31
Publication date: 2011-06-30
Also published as: KR20110073806A; KR101221815B1

Abstract

A preparation method of a brominated diphenylethane mixture according to the present invention comprises the following steps of: injecting a catalyst into a reactor where a moisture-removed solvent and diphenylethane are mixed; dropping a bromine solution into the reactor to react the obtained mixture; removing the catalyst from a reaction mass where the reaction terminates; distilling the catalyst-removed reaction mass to obtain a water-dispersed brominated diphenylethane mixture; and filtering and drying the water-dispersed brominated diphenylethane mixture.

Description

Process for preparing brominated diphenylethane mixture

The present invention relates to a process for the preparation of brominated diphenylethane mixtures. More specifically, the present invention relates to a continuous process for producing a brominated diphenylethane mixture having excellent yield and purity and improved transparency.

In general, brominated diphenylethane mixtures have been used as flame retardants for thermoplastic resin compositions or thermosetting resin compositions processed at high temperatures due to their excellent flame retardancy and thermal stability. In particular, brominated diphenylethane-based flame retardants are used in various products because they can obtain excellent flame retardant effect even in a small amount due to high bromine content.

Decabromodiphenylethane having 10 bromine substitutions in a diphenylethane flame retardant is disclosed in US Pat. Nos. 5,008,477, 5302,768, 5,324,874, 5,401,890, 5,457,248 and 7,129,384. have. However, decabromodiphenylethane lowers the impact strength of the used system due to the high dissolution temperature and low compatibility, and reduces the flowability, thereby limiting the applicable polymer.

U.S. Patent 5,055,235 discloses a method of substituting an average of 7 bromines per molecule of diphenylethane to improve the compatibility, which is a disadvantage of decabromodiphenylethane. The patent discloses a method for producing partially brominated diphenylethane by combining two catalysts, such as zirconium / aluminum trichloride and iron trichloride / aluminum trichloride, dispersed in methylene bromide with diphenylethane and adding bromine.

U.S. Patent No. 5,039,729 disperses aluminum chloride in methylene bromide, cools to 5 to 20 ° C, and then bromines at 0 to 60 ° C for 1 to 2.5 hours to substitute an average of 6.8 to 7.2 bromine per molecule of diphenylethane. Disclosed is a technique to make.

Japanese Patent Application Laid-Open No. 10-158202 discloses a method for producing diphenylethane bromide by dissolving diphenylethane and Lewis acid catalyst in a methyl chloride solvent to drop chlorine bromide.

However, the brominated compound obtained by the above method has a yellow property, which is not suitable for use as a flame retardant of a transparent product.

Accordingly, the present inventors add a catalyst to the solvent and diphenylethane, which have been removed from water, react with dropwise addition of a bromine solution, and then remove the catalyst by a specific method, and then distill the reaction mass to obtain the final brominated diphenylethane mixture. It has begun to develop a manufacturing method having a transparent property.

It is an object of the present invention to provide a new process for the preparation of brominated diphenylethane mixtures which have colorless and transparent properties.

Another object of the present invention is to provide a method for preparing a brominated diphenylethane mixture which is easy to control the reaction.

It is another object of the present invention to provide a continuous process for the preparation of brominated diphenylethane mixtures with excellent yield and purity.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention provides a process for the preparation of brominated diphenylethane mixtures. The method comprises the steps of adding a catalyst to a reactor in which the solvent and the diphenylethane, which have been removed with water, are mixed; Bromine solution is added dropwise to the reactor for reaction; Removing the catalyst from the reaction mass in which the reaction is completed; Distilling the reaction mass from which the catalyst has been removed to obtain a water-dispersed brominated diphenylethane mixture; And filtering and drying the water-dispersed brominated diphenylethane mixture.

In an embodiment, the solvent is a halogenated C 1-4 alkanes. The solvent may be added 2 to 20 times the weight of diphenylethane. In addition, the solvent may be removed moisture by distillation, absorbent or a combination thereof.

In embodiments, the catalyst may be added at 0.1 to 20% by weight relative to the weight of diphenylethane.

In a specific example, the dropwise addition of the bromine solution can be added dropwise at -30 to 30 ° C for 2 to 20 hours. In another embodiment, after the dropping, the reactor temperature may be increased to 40 to 90 ° C., and then aged for 2 to 20 hours.

In an embodiment, the catalyst removal can be removed by a wet process, a dry process or a combination thereof. The wet process includes adding and stirring an aqueous hydrochloric acid solution to the reaction mass, and then separating the lower layer including the solvent and the product. In the dry process, the catalyst may be removed by adding a catalyst remover and a neutralizer to the reaction mass.

In an embodiment, the solvent may be removed by adding a surfactant and an antifoaming agent during the distillation of the reaction mass from which the catalyst is removed.

In addition, the distilled aqueous dispersion brominated diphenylethane mixture may further comprise the step of aging (80) at 80 to 100 ℃ for 2 to 20 hours. In a specific embodiment, an aqueous hydrochloric acid solution may be added to the distilled aqueous dispersion brominated diphenylethane mixture to be aged.

FIG. 1 is a schematic process diagram of a process for preparing the brominated diphenylethane mixture of the present invention.

2 compares the colors of brominated diphenyl ethane prepared according to Example 1 and Comparative Example 1.

Method for producing a brominated diphenylethane mixture of the present invention is to put the catalyst in a reactor in which the solvent and the diphenyl ethane (DPE) is removed water; Bromine solution is added dropwise to the reactor for reaction; Removing the catalyst from the reaction mass in which the reaction is completed; Distilling the reaction mass from which the catalyst has been removed to obtain a water-dispersed brominated diphenylethane mixture; And filtering and drying the water-dispersed brominated diphenylethane mixture.

Water removal and bromination reaction process

The solvent used for the reaction completely removes the moisture before adding the catalyst. When water is removed from the solvent, most of the water is first removed by distillation, and then a residual amount of water may be removed using an absorbent.

The size of the reactor 2 in the distillation of the solvent is selected depending on the yield of the brominated diphenylethane mixture to be synthesized. The size of the reactor 2 is preferably 2-20 m 3 for industrial mass production, more preferably 5-15 m 3.

In embodiments, the reactor (2) is capable of temperature and pressure control to enable the bromination reaction with the distillation of the solvent, and use the one equipped with a condenser and a stirrer. In the embodiment, the reactor 2 is controlled to have a rotational speed of about 5 to 200 rpm, preferably 10 to 150 rpm, for mixing. It is not necessary to specify the form of the stirrer. In embodiments, the pressure in the reactor (2) can be adjusted to 0.1 to 800 torr, preferably to 500 to 770 torr. In addition, the corrosion of the reactor during the reaction is concerned, it is appropriate that the surface of the reactor is corrosion-resistant.

The reactor 2 uses a condenser 11 is provided. The condenser 11 may be installed in series or in parallel in multiple stages rather than in one stage, and has a minimum number of stages of two to ten stages, and may use cooling water having the same or different temperatures at each stage. desirable. The condenser preferably has an area of 6 to 80 m 2, more preferably 12 to 60 m 2. The temperature of the cooling water is allowed to be between -20 and 60 ° C in each condenser.

Each process temperature can be changed according to the solvent used, and the temperature is appropriately determined according to the boiling point of the solvent. Preferred solvents which can be used are halogenated C _1-4 alkanes. Specific examples include methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2- Tetra chloro ethane, methylene bromide, bromoform, carbon tetrabromide, 1,2-dibromoethane, 1,1,1-tribromoethane , 1,1,2,2-tetra bromoethane, bromochloroethane and the like. Among these, 1,2-dichloroethane is preferable.

After adding a solvent and diphenylethane to the reactor 2, the reactor temperature is increased to distill the solvent. The solvent is added to the reactor 2 about 2 to 20 times the weight of diphenylethane, preferably 5 to 15 times. The distillation rate of the solvent is 50 to 3000 kg / hr, preferably 100 to 2000 kg / hr is appropriate. The amount of diphenylethane reacted in one batch is 50 to 3,000 kg, preferably 100 to 2000 kg.

During solvent distillation, the water contained in the solvent and diphenylethane forms azeotrope with the solvent, so it is distilled to a high content at the beginning of the distillation. The distilled solvent is condensed in the condenser 11, only the solvent is refluxed to the reactor 2 in the oil / water separator, and H ₂ O is removed from the reaction system.

Generally, when 0-50% of the amount of added solvent is distilled to reflux, most of the solvent and water present in the diphenylethane are condensed and removed in the condenser. At this time, distillation is performed until the water content is 10 to 500 ppm, and an appropriate distillation amount is 2 to 30%. In an embodiment, the scrubber 1 may be connected to the condenser 11 to remove the halogenated acid generated during the reaction.

Thereafter, the solvent in which most H ₂ O is removed through the distillation may be further subjected to a process of removing a trace amount of water using an absorbent. Absorbers that can be used include PCl ₃ , POCl ₃ and the like.

The solvent and diphenylethane mixture from which the water is removed are cooled to -30 to 50 ° C., more suitably to -30 to 30 ° C., for the bromination reaction.

When the removal of the water is completed, the catalyst is added. The catalyst may be used in an amount of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the weight of diphenylethane to be reacted. The catalyst is for the bromination reaction, and any kind of metal salt Lewis acid can be used. Suitable catalysts include metals such as aluminum, iron, zirconium, titanium and antimony, reduced metals, halogenated metals, or mixtures thereof. Specific examples include Al, Fe, Zr, Ti, Sb, reduced Al, Fe, Zr, Ti, Sb or SbCl ₃ , SbCl ₅ , SbBr ₃ , SbClBr ₄ , SbBrCl ₄ , FeCl ₃ , FeBr ₃ , AlCl ₃ , Metal salt Lewis acids such as TiCl ₄ , TiBr ₄ , SnCl ₂ , SnBr ₃ , SnCl ₄ , AlBr ₃ , BeCl ₂ , CdCl ₂ , ZnCl ₂ , BF ₄ , BCl ₃ , BBr ₃ , BiCl ₃ , ZrCl _4, and the like. However, it is not necessarily limited thereto. The said catalyst can also be used individually or in mixture of 2 or more types.

Bromine solution is added dropwise to the reactor (2) to which the catalyst is added. The temperature at the time of reaction is -30-50 degreeC, More preferably, it is -30-30 degreeC, Most preferably, it is -20-30 degreeC. The dripping time is added in 2 to 20 hours, more preferably in about 2 to 8 hours. The amount of bromine solution added is preferably 6.1-6.5 times the weight of diphenylethane.

The bromine solution is prepared by adding bromine or bromine chloride to a chlorine-based organic solvent. During the reaction, Br _{2, which} is added to the reactant, is vaporized and released to the outside of the reaction system. Thus, the cooling water temperature of the condenser must be kept sufficiently low so that Br ₂ can be recovered and refluxed in the condenser.

After the dropping of the bromine solution is completed, the temperature of the reactor 2 may be raised to proceed aging. The aging may proceed in the same or different reactor as the bromination reactor (2). It is preferable to advance the said aging temperature to 40-90 degreeC, More preferably, it raises to 50-80 degreeC. The time required for the aging is appropriately about 2 to 20 hours, more preferably 2 to 8 hours. The HBr generated at this time is removed and the conditions are maintained such that Br ₂ and the solvent are refluxed.

Catalyst Removal Process

The reaction mass in which the reaction is completed removes the catalyst through a catalyst removal process. In the embodiment, the reactor 3 used in the catalyst removal process uses a reactor having a size of 3 to 30 m 3, and more preferably a reactor having a size of 5 to 20 m 3. The reactor (3) used for the catalyst removal can be temperature controlled to 50 ~ 90 ℃, so that the cooling and the temperature increase is selected. In addition, for the stirring of the reactor, the rotation speed of the Agitator is preferably about 5 to 200 rpm, more preferably 10 to 150 rpm. It is appropriate that the surface of the reactor is prevented from corrosion since the reactor may be corroded during washing. Catalyst removal can be removed by a dry process, a wet process, or a combination thereof.

The dry process is to remove the catalyst by adding a catalyst remover and a neutralizing agent to the transferred reaction mass. The catalyst remover and the neutralizer are added in an amount of 0.1 to 5.0 times the amount of catalyst added.

Examples of the catalyst removing agent are anhydrous salts or hydrates, halides of alkali metals such as NaCl, KCl, halides of alkaline earth metals such as MgCl ₂ , CaCl ₂ , or alkali metal salts of organic acids, alkaline earth metal salts of organic acids, and inorganic acids. Alkali metal salts and alkaline earth metal salts of inorganic acids can be used. Most preferably Sodium Acetate.

The neutralizing agent may be a conventional neutralizing agent well known to those skilled in the art, and generally, any chemicals capable of neutralizing acid may be used.

The wet process dissolves the catalyst used in the reaction by adding 2 to 35% aqueous hydrochloric acid solution to the reaction mass by adding 0.5 to 5.0 times the weight of diphenylethane. The temperature is maintained at 40 to 90 ° C, preferably 45 to 80 ° C. At this time, the mixture in the reactor 3 should be stirred at a sufficient speed so that the catalyst is sufficiently dissolved. The stirring time is suitably 1 to 20 hours. After stirring, the mixture in reactor 3 is separated into an upper layer comprising catalyst and water and a lower layer comprising solvent and reaction product. Depending on the reaction conditions, the two phases may form a partially mixed phase. In embodiments only the solution of the bottom layer may be transferred to another wash reactor for the second wash. The washing can be carried out 2-3 times until all the added catalyst is dissolved. In some cases, one wash reactor may be used if one wash is sufficient.

In the case of using a dry process and a wet process in combination, it is generally common to go through a dry process first and then perform a wet process.

Solvent distillation process

The reaction mass from which the catalyst is removed is subjected to distillation to remove the solvent.

The reactor 4 required to remove the solvent is capable of temperature and pressure control and uses a condenser and a stirrer. In the embodiment, the size of the reactor 4 is preferably 2-20 m 3, more preferably 3-15 m 3. The distillation rate is 50 to 3,000 kg / hr, preferably 100 to 2,000 kg / hr.

The reactor 4 uses a condenser 41 is provided. The condenser 41 is preferably installed in series or parallel connection in multiple stages rather than in one stage, and has a minimum number of stages of two to ten stages, and may use cooling water having the same or different temperatures at each stage. Do. The condenser preferably has an area of 6 to 80 m 2, more preferably 12 to 60 m 2. The temperature of the cooling water is allowed to be between -20 and 60 ° C in each condenser.

In the case of solvent distillation, a stirrer may be necessary for mixing the distillate. At this time, the speed of the stirrer is preferably 5 to 200 rpm, more preferably 10 to 150 rpm. In an embodiment the pressure in the reactor 4 is adjusted to 0.1 to 800 torr, preferably 500 to 770 torr for distillation conditions. It is appropriate that the surface of the reactor is corrosion-protected because of the corrosion of the reactor during the reaction.

The reaction mass from which the catalyst has been removed is introduced into the reactor (4), and 0.2 to 5.0 times of water relative to the solvent is put in a solvent distillation reactor and heated to 70 to 100 ° C. In embodiments, surfactants and antifoams may be added. The surfactant may be added 0.001 to 5% by weight of the H ₂ O added. The surfactant may be anionic, cationic and nonionic as ionic, and examples thereof include Perfluorooctanoate (PFOA or PFO), Perfluorooctanesulfonate (PFOS), Sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, and other alkyl sulfate salts, Sodium laureth sulfate, also known as sodium lauryl ether sulfate (SLES), Alkyl benzene sulfonate, Soaps, or fatty acid salts, Cetyl trimethylammonium bromide (CTAB) aka hexadecyl trimethyl ammonium bromide, and other alkyltrimethylammonium salts, Cetylpyridinium chloride (CPC), Polyethoxylated tallow amine (POEA), Benzalkonium chloride (BAC), Benzethonium chloride (BZT), Dodecyl betaine, Cocamidopropyl betaine, Coco ampho glycinate, Alkyl poly (ethylene oxide), Alkylphenol poly (ethylene oxide), Copolymers of poly (ethylene oxide) and poly (propylene oxide) (commercially called Poloxamers or Poloxamines), Octyl glucoside, Decyl maltoside, Fatty alcohols, Cetyl alcohol, Oleyl alcohol, Cocamide MEA, co Camide DEA, Polysorbates: One or a mixture of two or more common surfactants such as Tween 20, Tween 80, and Dodecyl dimethylamine oxide can be used. Preferably, anionic surfactants are used.

The antifoaming agent is preferably added 0.0005 to 5% by weight based on the H ₂ O weight. As the antifoaming agent, a conventional antifoaming agent may be used. Examples thereof include mineral oil, vegetable oil, white oil, long-chain fatty alcohol, fatty acid soap or fatty acid ester, copolymer of polyethylene glycol or polypropylene glycol, silicon oil, silicon glycol or modified Silicon fluid and the like can be used. Most suitably, silicon-based fluids are preferred in terms of efficiency.

After performing solvent distillation for 1 to 20 hours as described above, a brominated diphenylethane mixture finally dispersed in H ₂ O can be obtained.

The distilled water-dispersible brominated diphenylethane mixture may be further subjected to aging at 80 to 100 ° C. At this time, an aqueous solution of 2 to 35% hydrochloric acid may be added in an amount of 1 to 20% based on the weight of the brominated diphenylethane mixture. The aging time is preferably 2 to 20 hours. All residual solvent is removed through the aging process. The aging brominated diphenyl ethane mixture aqueous solution is cooled to 30-60 degreeC.

Filtration and drying process

The aqueous solution of brominated diphenylethane mixture having been distilled off is filtered and dried in a conventional manner. The filtration is possible as long as it is a filter system that can be generally used, such as a conventional filter system, Nutche-Filter, Filter Press, ANT Filter System. The filter paper uses one having a pore sized to filter the brominated diphenylethane mixture produced during the process. The aqueous dispersion brominated diphenylethane mixture transferred to the filter system is filtered to separate the water and brominated diphenylethane mixture. The separated brominated diphenylethane mixture is in the form of a wet-cake, in which an appropriate amount of H ₂ O is added thereto and subjected to secondary filtration. The process may be repeated until the pH of the H ₂ O filtered in the Filter System reaches 7.

The filtered wet cake is transferred to a dryer and dried at 100 to 130 ° C. for 5 to 30 hours. The drying process is a drying time and conditions vary depending on the type or size of the dryer, but generally there is no problem when using a dryer that is industrially used.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

실시예 1Example 1

5 ㎥3000 kg of 1,2-dichloroethane and 253.7 kg of diphenylethane were added to the reactor, and the reactor temperature was raised to 80 ° C to distill 1,2-dichloroethane. After distilled 1,2-dichloroethane was condensed in the condenser installed in the reactor, only 1,2-dichloroethane was refluxed through the oil / water separator and water was removed from the reaction system. 15 kg of a reduced Fe powder catalyst was added to a mixture of 1,2-dichloroethane and diphenylethane distilled at a water content of 500 ppm or less, and the reactor temperature was cooled to 0 ° C. 750 kg of bromine was added dropwise to the reactor over 6 hours, and then the reactor temperature was raised to 50 ° C. and aged for 4 hours. After this, the reaction mass is 8 ㎥After transfer to a size catalyst removal reactor, 300 kg of water and 200 kg of 30% HCl aqueous solution were added and stirred at a speed of 120 rpm for 2 hours at a temperature of 70 ° C, followed by standing for 1 hour to separate the two layers. Confirmed. After separating the 1,2-dichloroethane and the product mixture solution formed in the lower layer was repeated the above process. The 1,2-dichloroethane and the product mixed solution is 8 ㎥1500 kg of water was added to the distillation reactor of the size, and distillation was slowly added at 95 ° C. for 8 hours. The water-dispersed brominated diphenylethane mixture was then aged at 95 ° C. for 5 hours and then cooled to 50 ° C. The cooled aqueous dispersion brominated diphenylethane mixture was filtered twice to obtain a brominated diphenylethane mixture on a wet cake, which was dried at 110 ° C. for 7 hours. The dried final brominated diphenylethane mixture had milky white particles.

비교실시예 1Comparative Example 1

5 ㎥3000 kg of 1,2-dichloroethane and 253.7 kg of diphenylethane were added to the reactor, and the reactor temperature was raised to 80 ° C to distill 1,2-dichloroethane. After distilled 1,2-dichloroethane was condensed in the condenser installed in the reactor, only 1,2-dichloroethane was refluxed through the oil / water separator and water was removed from the reaction system. ZrCl in 1,2-dichloroethane and diphenylethane mixture distilled to 500 ppm or less₄ 15 kg of catalyst was added and the reactor temperature was maintained at 60 ° C. 750 kg of bromine was added dropwise to the reactor over 6 hours and then the reactor temperature was raised to 70 ° C. and aged for 4 hours. After this, the reaction mass is 8 ㎥After transfer to a size catalyst removal reactor, 300 kg of water and 200 kg of 30% HCl aqueous solution were added and stirred at a speed of 120 rpm for 2 hours at a temperature of 70 ° C, followed by standing for 1 hour to separate the two layers. Confirmed. After separating the 1,2-dichloroethane and the product mixture solution formed in the lower layer was repeated the above process. The 1,2-dichloroethane and the product mixed solution is 8 ㎥1500 kg of water was added to the distillation reactor of the size, and distillation was slowly added at 95 ° C. for 8 hours. The water-dispersed brominated diphenylethane mixture was then aged at 95 ° C. for 5 hours and then cooled to 50 ° C. The cooled aqueous dispersion brominated diphenylethane mixture was filtered twice to obtain a brominated diphenylethane mixture on a wet cake, which was dried at 110 ° C. for 7 hours. The dried final brominated diphenylethane mixture had yellowish white particles.

Brominated diphenyl ethane prepared according to Example 1 and Comparative Example 1 is shown in Figure 2 to compare the color.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

Adding a catalyst to a reactor in which water-removed solvent and diphenylethane were mixed;

Bromine solution is added dropwise to the reactor for reaction;

Removing the catalyst from the reaction mass in which the reaction is completed;

Distilling the reaction mass from which the catalyst has been removed to obtain a water-dispersed brominated diphenylethane mixture; And

Filtering and drying the water-dispersed brominated diphenylethane mixture;

Method for producing a brominated diphenylethane mixture, characterized in that comprising a step.
The method of claim 1, wherein the solvent is a halogenated C 1-4 alkanes, characterized in that 2 to 20 times the weight of the diphenylethane.
The method of claim 1, wherein the water-removed solvent is water is removed by distillation, absorbent or a combination thereof.
The method of claim 1, wherein the catalyst is added in an amount of 0.1 to 20% by weight based on the weight of diphenylethane.
The method according to claim 1, wherein the dropping is carried out at -30 to 30 ° C for 2 to 20 hours.
The method of claim 5, wherein the dropping temperature of the reactor to 40 ~ 80 ℃ after aging (aging) for 2 to 20 hours.
The method of claim 1 wherein the catalyst removal is removed by a wet process, a dry process or a combination thereof.
The method of claim 7, wherein the wet process comprises adding and stirring an aqueous hydrochloric acid solution to the reaction mass to separate the lower layer including the solvent and the product.
The method of claim 7, wherein the dry step is characterized by removing the catalyst by adding a catalyst remover and a neutralizing agent to the reaction mass.
The method of claim 1, wherein the solvent is removed by adding a surfactant and an antifoaming agent during the distillation of the reaction mass from which the catalyst is removed.
The method of claim 10, wherein the distilled water-dispersed brominated diphenylethane mixture is aged at 80-100 ° C. for 2-20 hours.
12. The method according to claim 11, wherein an aqueous hydrochloric acid solution is added to the distilled aqueous dispersion brominated diphenylethane mixture to aging.