KR101460681B1 - Methods for Low temperature synthesis of an Aromatic Phosphate Ester Compound and the Device Thereof - Google Patents

Abstract

The present invention relates to a process for the preparation of novel aromatic phosphoric acid ester compounds comprising the steps of: (a) reacting (i) a compound represented by the following formula (1) and (ii) hydroxy or C _1-6 alkoxy a C _6-10 aryl, or substituted by hydroxy or C _1-6 alkoxy C _6-20 aryl compound using a temperature 90-125 ℃, 125-180 ℃ substituted with, 180-210 and 210-240 ℃ ≪ RTI ID = 0.0 > C, < / RTI > (b) separating the aromatic phosphoric acid ester compound from the product of step (a) by fractional distillation under the conditions of a temperature of 50 ° C to 300 ° C and a pressure of 0.01 mmHg to 50 mmHg; And (c) reacting (i) the aromatic phosphoric acid ester compound separated in step (b) and (ii) an alcohol or nitrogen compound of C ₁ -C ₁₀ at 10-60 ° C. The manufacturing method of the present invention minimizes the loss of raw materials by utilizing a multi-stage heating system and a reflux system, and can prevent an explosion in the production of a highly reactive compound by using a dual cooling system using thermal oil and water, Can be used to obtain a compound of high purity. Thus, the amount of flame retardant used in the flame retarding treatment can be adjusted to an appropriate amount, and it can be used not only for general textile products but also for flame retarding treatment of some products requiring safety / toxicity test.

Description

TECHNICAL FIELD The present invention relates to a low-temperature synthesis method of an aromatic phosphoric acid ester compound,

The present invention relates to a method and apparatus for low temperature synthesis of aromatic phosphoric ester compounds.

Thermosetting resins such as polypropylene, polystyrene, and polyester resins and thermosetting resins such as polyurethane or phenol resin can be manufactured at relatively low cost and have excellent characteristics that can be easily molded. Therefore, these resins are widely used throughout household goods including electronic parts and automobile parts.

However, these thermoplastic resins and thermosetting resins are disadvantageous in that they easily burn or disappear when a fire occurs. In particular, fires in public facilities such as electrical facilities and telecommunication cables can cause major damage to social functioning. In order to improve the above disadvantages, in some fields such as electric appliances, automobile interior parts, and textile products in which the resin is used, flame retardation is legally prescribed.

In order to provide the resin with flame resistance, a flame retardant is generally added in the production of a resin product, and an inorganic compound, an organic phosphorus compound, an organic halogen compound, and an organic phosphorus compound containing a halogen are used as a flame retardant. Among these compounds, the organic halogen compound and the halogen-containing organic phosphorus compound show excellent flame retarding effect.

However, these compounds generate hydrogen halide which causes problems such as deterioration and coloring of the corrosion resin itself of the molded metal by pyrolysis when molding the resin product. In addition, since hydrogen halide is a poisonous substance, it not only deteriorates the work environment but also generates a toxic gas such as hydrogen halide and dioxine in the event of a fire, thereby adversely affecting the human body. Inorganic compounds such as magnesium hydroxide and aluminum hydroxide are known as halogen-free flame retardants, but they are required to be added in a large amount in order to obtain a sufficient flame-retarding effect, resulting in deterioration of the physical properties of the resin itself.

Organophosphorus compounds are generally used as flame retardants exhibiting a comparatively good flame retarding effect for the above reasons, and aromatic compounds such as triphenylphosphate (TPP), tricresyl phosphate (TCP) and cresyldiphenylphosphate (CDP) . In general, TPP is used as a mixture with a halogen compound in order to exhibit flame retardancy.

As a method for producing a flame retardant containing the organophosphorus compound, Korean Patent Publication No. 1994-0011789 discloses a flame retardant for a polyethylene terephthalate ester fiber fabric and a method for producing the flame retardant. In particular, the above-mentioned prior art discloses a method for producing an aromatic phosphoric acid ester compound (DPPAP) which functions as a flame retardant, but the method is not largely deviated from existing methods which are difficult to synthesize, The specific conditions such as the present invention are not provided for the pressure range and the separation method of the target compound.

Accordingly, it is an object of the present invention to provide a process for preparing an aromatic phosphoric acid ester compound having a flame retarding effect, which can obtain a compound having a high yield.

Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

The present inventors have made extensive efforts to develop a process for producing a novel aromatic phosphoric acid ester compound which is a raw material for a flame retardant. As a result, the present inventors have developed a process for producing an aromatic phosphate ester compound capable of inducing the synthesis of a compound at the highest yield through a multi-stage heating system and a reflux circulation system. And by using a dual cooling system using thermal oil and water, it is possible to prevent the explosion risk in the case of producing a compound having high reactivity and to obtain a compound with high purity by separating the compound using fractional distillation. Thereby completing the invention.

 Accordingly, an object of the present invention is to provide a novel process for producing an aromatic phosphate ester compound.

It is another object of the present invention to provide a novel dual cooling system.

It is another object of the present invention to provide a novel method for synthesizing a compound.

It is another object of the present invention to provide a novel fractionation process.

It is another object of the present invention to provide a novel compound low temperature synthesis method.

Still another object of the present invention is to provide a novel double cooling apparatus.

It is still another object of the present invention to provide a novel compound synthesis apparatus.

It is another object of the present invention to provide a novel fractionation apparatus.

It is another object of the present invention to provide a novel compound low temperature synthesis apparatus.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a process for producing an aromatic phosphoric acid ester-based compound comprising the steps of:

(a) as a reactant (ⅰ) The following compounds represented by formulas (1) and (ⅱ) hydroxy or C _1-6 alkoxy substituted by a C _6-10 aryl group, or a hydroxy or C _1-6 alkoxy substituted with C Reacting a _6-20 arylalkyl compound by heating at a temperature of 90-125 ° C, 125-180 ° C, 180-210 ° C, and 210-240 ° C in succession;

(b) separating the aromatic phosphoric acid ester compound from the product of step (a) by fractional distillation under the conditions of a temperature of 50 ° C to 300 ° C and a pressure of 0.01 mmHg to 50 mmHg; And

(c) reacting (i) the aromatic phosphoric acid ester compound separated in step (b) and (ii) an alcohol or nitrogen compound of C ₁ -C ₁₀ at 10-70 ° C;

Formula 1

Wherein R ₁ , R ₂ and R ₃ are each independently (i) halo, (ii) C _6-10 aryl substituted by hydroxy or C _1-6 alkoxy, or (iii) hydroxy or C _{& Lt} ; RTI ID = 0.0 > _C6-20 < / RTI > arylalkyl substituted with _1-6 alkoxy; At least _{one of} R ₁ , R ₂ and R ₃ is halo.

The present inventors have made extensive efforts to develop a novel aromatic phosphoric acid ester compound, and as a result, have found that a method for producing an aromatic phosphate ester compound capable of inducing the synthesis of a compound at the highest yield through a multistage heating system and a reflux circulation system Respectively. The conventional process for producing a phosphate ester compound has a disadvantage in that the yield is low. The present inventors have tried to develop a process for improving the process, and as a result, the process of the present invention has been designed. The present inventors have found that by using the reflux system, the production method minimizes the loss of raw materials, and by using a dual cooling system using thermal oil and water, it is possible to prevent the explosion risk in the production of a compound having high reactivity, And it was confirmed that a high-purity compound can be obtained by separation.

In the process for producing an aromatic phosphoric acid ester compound of the present invention, stepwise compound synthesis reaction takes place by heating step 4, and in the synthesis reaction at each temperature step, reflux occurs, So that it can participate in the synthesis reaction of the compound. Further, in the production method of the present invention, the temperature change of the reaction system (for example, the reaction vessel or the distillation apparatus) is measured at each heating step, thereby clearly knowing when to raise the temperature to the next step temperature, thereby minimizing the production time.

Hereinafter, a method for producing an aromatic phosphoric acid ester compound according to the method of the present invention will be described in detail.

Step (a): heating the reactants

First, as the reaction material (ⅰ) a C _{6 -20} substituted with a C _{6 -10} aryl, or a hydroxy or C _{1 -6} alkoxy substituted compounds, and (ⅱ) hydroxy or C _{1 -6} alkoxy group represented by the formula (1) The reaction is carried out by sequentially heating at a specific temperature range using an arylalkyl compound.

The above formula (1) is represented as follows:

Formula 1

In Formula 1, R ₁ and R ₂ And R ₃ is a substituted C ₆ to each independently (ⅰ) halo, (ⅱ) hydroxy-C _{1 -6} or substituted C _{6 -10} aryl-alkoxy, or (ⅲ) hydroxy or C _{1 -6 alkoxy- 20} arylalkyl; Wherein R ₁ , R ₂ And R < ₃ > is halo.

In the present specification, the term " halo " used to define the compound of formula (1) represents a halogen group element and includes, for example, fluoro, chloro, bromo and iodo, preferably chloro.

As used herein, the term " alkoxy " means an -O alkyl group and includes, for example, ethoxy, methoxy and the like, and when the C _1-6 alkoxy is substituted, the number of carbon atoms of the substituent is not included.

As used herein, the term " aryl " refers to a substituted or unsubstituted monocyclic or polycyclic carbon ring that is totally or partially unsaturated. C _{6 -10} aryl group is not included in the carbon number of the substituent when the aryl group means a group having a carbon ring atom of a carbon number of 6 to 10, C _{6 -10} aryl-substituted. Preferably the aryl is monoaryl or biaryl. The monoaryl preferably has from 5 to 6 carbon atoms, and the biaryl preferably has from 9 to 10 carbon atoms. Most preferably, the aryl is substituted or unsubstituted phenyl. Monoaryl, e.g., in the case where the substituted phenyl, the substitution can be made by a variety of substituents at various positions, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₆ Substituted or unsubstituted straight-chain or branched alkyl or C ₁ -C ₆ Lt; / RTI > may be substituted by straight chain or branched alkoxy. Preferably said aryl is unsubstituted phenyl.

As used herein, the term "C _{6 -20} aryl-alkyl" refers to an alkyl group substituted with an aryl group. C _{6 -20} aralkyl group is not included in the carbon number of the substituent, and when a mean aralkyl having the aralkyl unit having 6 to 20, C _{6 -20} aralkyl is optionally substituted. Aryl in the aralkyl group is preferably a monoaryl or biaryl, alkyl is preferably a C _{1 -3} alkyl, more preferably C ₁ alkyl. Aryl in the aralkyl may be optionally substituted with various substituents at various positions, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₄ Substituted or unsubstituted straight or branched chain alkyl, C ₁ -C ₄ Straight chain or branched chain alkoxy, alkylcarbamoyl, or a combination thereof.

According to a preferred embodiment of the present invention, R ₁ , R ₂ And R ₃ are each independently (ⅰ) halo, (ⅱ) hydroxy or C _{1 -3} aryl C ₆ alkoxy, or (ⅲ) hydroxy C _{1 -3} or a C _6-10 alkoxy substituted with aryl Alkyl.

The reaction temperature of step (a) is in the range of 90-125 ° C, 125-180 ° C, 180-210 ° C and 210-240 ° C, preferably 95-120 ° C, 135-180 ° C, 210-240 占 폚, more preferably 100-120 占 폚, 140-180 占 폚, 185-200 占 폚, and 220-240 占 폚.

One of the greatest features of the present invention is that the compound synthesis reaction is induced through a multistage heating method unlike the conventional synthesis of a phosphoric acid ester compound having a flame retardant effect and when the unreacted compound is present, And thus the loss of raw materials can be minimized.

As used herein, the term " reflux " broadly means distillation, which means that the compound vapor rises along the distillation column and then condenses back into liquid to flow down the inner wall of the distillation column. That is, reflux is an action for increasing the synthesis reaction in the reaction vessel. In the reaction for synthesizing the compound of step (a) of the present invention, the reflux circulation of the reactant or the reaction product of the step (a) occurs in the respective temperature ranges to be heated.

According to a specific embodiment of the present invention, a mixture of phosphorus oxychloride (POCl ₃ ) and phenol can be heated to a temperature of 102 ° C to produce PDCP, DPCP and TPP. However, unreacted phosphorus oxychloride and phenol may remain in the reaction material within the above temperature range, and the unreacted reactants may induce the reaction by heating again to the boiling point of phenol and phosphorus oxychloride. In this case, the compound vapors of the reactants are recovered to the reaction vessel through which the compound synthesis reaction takes place through the reflux process.

Step (b): Separation of aromatic phosphoric ester compounds

The aromatic phosphoric acid ester compound is then separated from the product of step (a) using fractional distillation under specific temperature and pressure conditions.

As used herein, the term " fractional distillation " is a method for separating a mixture containing various compounds by boiling point difference, and separating the mixture using a fractionation tower. As the mixture rises above the fractionation tower, substances with similar boiling points are collected and separated again into a pure substance.

The heating temperature range for the fractional distillation is carried out at 300 DEG C or less considering the material inside the distiller in which the fractional distillation is performed. Since the inside of the distiller is coated with glass or carbon, it is preferable to carry out fractional distillation in the temperature range of 300 DEG C or less. More preferably, the temperature range in which the fractional distillation is carried out is 50 ° C to 300 ° C. More preferably, step (b) will be carried out near the boiling point of each compound separated as the fractional distillation. For example, in the examples of the present invention, the boiling points of PDCP, DPCP and TPP synthesized due to the reaction of phosphorus oxychloride and phenol are 241-243 ° C (at 760 mmHg), 314-316 ° C (at 488 mmHg) 245 < 0 > C (at 11 mmHg), and the compounds can be heated to the boiling point to separate each compound at each boiling point.

However, the fractional distillation must be performed at a temperature of 300 ° C or less in consideration of the material inside the distiller in which the fractional distillation is performed. Therefore, the reduced pressure in the still is indispensably required. The depressurization process may be performed by various known depressurization devices, for example, the depressurization process may be performed by a vacuum pump connected to the distillation-distillation column. By forming a vacuum state near the vacuum by the vacuum pump, the boiling point of the compound to be separated can be reduced. Preferably, the fractional distillation is carried out at a pressure of 0.01 mmHg-50 mmHg, more preferably 0.1 mmHg-35 mmHg, even more preferably 0.1 mmHg-20 mmHg, even more preferably 1 mmHg-20 mmHg. < / RTI >

The compound separated by the step (b) may be transferred to the compound synthesis step (a) to participate in the additional reaction. For example, the PDCP separated by the fractional distillation may go to step (a) and react with phenol additionally to produce DPCP.

Step (c): Low temperature synthesis of aromatic phosphate ester compounds

The aromatic phosphoric acid ester compound and C ₁ -C ₁₀ alcohol or nitrogen compound separated in step (b) are reacted at a low temperature to synthesize the final aromatic phosphoric acid ester compound.

As used herein, the term " alcohol " means a compound wherein the hydroxyl group is bonded to the carbon atom of the alkyl or substituted alkyl group. C ₁ -C ₁₀ Alcohol means an alcohol compound having an alcohol unit having 1 to 10 carbon atoms, and when the C _{1 -10} alcohol is substituted, the number of carbon atoms of the substituent is not included. Preferably, the alcohol is a C _{1 -5} alcohol, more preferably a C _{1 -3} alcohol.

As used herein, the term " nitrogen compound " is a compound containing the element " nitrogen (N) ", and includes, for example, propylamine, butylamine, pentamine, hexamine. Amine.

The aromatic phosphoric acid ester compound separated in the step (b) contains an acidic gas (for example, chlorine gas) and exhibits an explosive exothermic reaction with an alcohol or a nitrogen compound. Therefore, the nitrogen compound should be added while dropping, and the heat generated in the reaction should be cooled, and the synthesis reaction in the step (c) is carried out at a low temperature. The lower temperature range is preferably 10 ° C to 70 ° C, more preferably 10 ° C to 50 ° C, even more preferably 10 ° C to 40 ° C, even more preferably 20 ° C to 35 ° C to be.

According to a preferred embodiment of the present invention, since the reaction product of step (c) contains a large amount of an acidic gas such as chlorine gas, it is difficult to immediately use the reaction product of step (c) itself as a flame retardant. Accordingly, after the step (c), the step of neutralizing the reaction product of step (c) may be further included. In the neutralization step, neutralization can be performed using a basic compound such as NaOH.

In the neutralization step, by-products (salt and H ₂ O) generated by the neutralization reaction are generated, and a step for removing the byproducts may be additionally included. For example, NaCl produced by the reaction of NaOH and chlorine gas can be removed by adding ethanol, methanol or toluene as a solvent, and the organic solvent can be removed by a subsequent dehydration reaction. On the other hand, the by-product H ₂ O by the neutralization reaction can be removed by a drying process such as vacuum drying.

The method for producing an odorant phosphate compound of the present invention may further include a step for cooling the compound generated in the compound reaction or the fractional distillation in the steps (a) to (c).

According to a preferred embodiment of the present invention, in order to cool the heat generated during the compound reaction or the fractional distillation of the step (a) to the step (c), (i) using a heat medium oil or silicone oil as a cooling fluid, Condensing the vapor of the vaporized compound in steps (a) to (c), and (ii) cooling the heated thermal oil using water as cooling fluid and heating in step (i) System. In the dual cooling system, heat generated during reflux of the heat medium flow path compound is cooled instead of cooling water. This is a safeguard against explosion hazards in the manufacture of highly reactive compounds. If the cooling fluid in the cooler is leaking, if the cooling fluid is water, heat oil or silicone oil is used instead of cooling water because explosion reaction may occur due to reaction with the compound. The heated thermal oil is again cooled by moving to a cooler containing cooling water.

According to a preferred embodiment of the present invention, the aromatic phosphoric acid ester compound produced by the production method of the present invention is represented by the following Chemical Formulas 2 to 5:

(2)

(3)

Formula 4

Formula 5

According to another aspect of the present invention, the present invention provides a dual cooling system comprising the steps of:

(a) a first step of cooling a target material to be cooled using thermal oil or silicone oil as a cooling fluid; And

(b) a second step of using water as a cooling fluid and cooling the heating fluid heated in the first cooling step.

The cooling fluid passes through the inside of the cooler and takes away heat generated in the cooler and conveys it to the outside. As the cooling fluid, various known materials can be used. In the present invention, thermal oil or silicone oil and cooling water are used.

According to a preferred embodiment of the present invention, the object to be cooled in step (a) is a substance having high reactivity with water. For example, when a material having high reactivity with water is cooled through the cooling water, there is a risk of explosion as reaction of the cooling water with the target material occurs when leakage of the cooler occurs. Therefore, in order to prevent the explosion risk, a dual cooling system may be used in which the target material is cooled using relatively low heat transfer oil and the heat oil is heated by cooling water.

The object substance is a reactive substance, which is a reactive substance, which is decomposed by a slight energy, is an unstable substance that causes combustion or explosion, or a natural substance that easily fires upon contact with air, water, or the like. A chemical substance that is highly reactive, such as a hazardous substance.

According to another aspect of the present invention, the present invention provides a method for synthesizing a compound comprising the steps of:

(a) heating and reacting two or more reactants;

(b) condensing and refluxing the vaporized vapor of the reactant and the reaction product of step (a); And

(c) cooling the heat generated in the step (a) and the step (b), wherein (i) a thermal oil or a silicone oil is used as the cooling fluid, and Condensing the vapor of the vaporized compound, and (ii) using water as the cooling fluid and cooling the heated thermal oil in step (i).

According to a preferred embodiment of the present invention, the compound synthesis method is carried out in a reaction vessel whose inner wall is coated with glass or carbon.

Hereinafter, a method for synthesizing a compound according to the method of the present invention will be described in detail.

Step (a): heating the reactants

First, two or more reactants are heated to induce a synthesis reaction. The heating temperature can be determined by considering the boiling point of the reactant.

Step (b): Refluxing of the reactants and the reaction product

The reactants and reaction products of step (a) vaporize and rise when they reach the boiling point of the materials. These compound vapors contain unreacted reactants and are refluxed to participate in the reaction again. That is, the vapor of the compound is cooled and condensed to recover the reaction system, in which the compound synthesis reaction can occur again.

Step (c): Cooling

The heat generated in the steps (a) and (b) is cooled. The cooling process utilizes a dual cooling system, i.e., (i) condensing the vapor of the vaporized compound in steps (a) through (b) using thermal oil or silicone oil as the cooling fluid, and ) ≪ / RTI > using water as the cooling fluid and cooling the heated fluid oil in step (i).

As described above, the method for synthesizing the compound of the present invention is described as being performed stepwise as a step of heating the reaction material, refluxing, and cooling by the double cooling system of the vaporized compound. However, The heating, refluxing and cooling processes may be performed in sequence, and (ii) the heating, refluxing, and cooling processes may be performed at the same time.

According to another aspect of the present invention, the present invention provides a fractional distillation process comprising the steps of:

(a) reducing a pressure of a reaction system containing a reaction product containing two or more compounds and chlorine gas using a vacuum pump;

(b) collecting the chlorine gas contained in the reaction product from the decompression process of step (a);

(c) heating at least two compounds contained in the product of step (a) from which chlorine gas has been removed; And

(d) cooling and condensing the vaporized compound vapor from the compound of step (c).

According to a preferred embodiment of the present invention, the fractional distillation method is carried out in a distiller whose inner wall is coated with glass or carbon.

Hereinafter, the fractional distillation method according to the present invention will be described in detail.

Step (a): Decompression step

First, the pressure of the reaction system containing the reaction product containing two or more compounds and chlorine gas is reduced by using a vacuum pump.

The depressurization process is carried out for boiling point lowering of the two compounds and chlorine gas separation. The fractional distillation process is carried out in a distiller whose inner wall is coated with glass or carbon, as described above, and therefore should be carried out at a temperature of 300 ° C or lower. Therefore, a decompression process for lowering the boiling point of the compound to be separated is indispensably required.

Step (b): Chlorine gas capture

Then, the chlorine gas contained in the reaction product is collected from the decompression process of the step (a). The chlorine gas that has passed through the vacuum pump due to the decompression process in step (a) can be stored in a separate storage tank. The collected chlorine gas can be stored in H ₂ O and stored or neutralized with NaOH. In the present invention, steps (a) and (b) are separately described. However, this is for convenience of description, and chlorine gas collection may be performed simultaneously with the decompression process.

Step (c): heating

Two or more compounds contained in the chlorine gas-removed product of step (a) are heated to the boiling point of each compound. The boiling point of the compound is lowered due to the decompression process of step (a), and the vapor of the compound is generated when the boiling point is lowered.

Step (d): Cooling

The vaporized compound vapor from the compound of step (c) is cooled and condensed. The condensed compound is stored in a separate storage vessel and is the final compound separated by the fractional distillation method of the present invention.

According to another aspect of the present invention, the present invention provides a compound low temperature synthesis method comprising the steps of:

(a) reacting two or more reactants at 10-70 占 폚 with stirring;

(b) cooling the heat generated in the reaction of step (a) to maintain the reaction temperature at 10-70 캜;

(c) neutralizing the reaction product of step (b); And

(d) removing H ₂ O and salts produced as a result of the neutralization reaction of step (c).

Hereinafter, the method for synthesizing a compound according to the present invention will be described in detail.

Steps (a) and (b): Low temperature stirring and reaction

First, two or more reactants are reacted by stirring at 10-70 ° C. The reason why the compound is synthesized at a low temperature is that the reactivity between the reactants is very high and explosive reaction occurs, and decomposition or discoloration of the compound occurs at a temperature of 70 ° C or higher. In addition, when the temperature of the reaction vessel in which the synthesis reaction occurs due to the heat generated in the reaction increases, the reaction vessel may melt, rupture or crack. Therefore, at the time of the low-temperature synthesis, a separate cooling step for maintaining the temperature of the reaction system in which the synthesis reaction of the reactant occurs is kept at a low temperature. The heat generated in the reaction of step (a) is cooled, and the reaction is continued at a reaction temperature of 10-70 ° C.

The reaction temperature is preferably from 10 ° C to 70 ° C, more preferably from 10 ° C to 50 ° C, even more preferably from 10 ° C to 40 ° C, even more preferably from 20 ° C to 35 ° C.

Step (c): neutralization

Next, the reaction product of step (b) is neutralized. For example, HCl, H ₂ SO ₄ , HNO ₃ and CH ₃ COOH can be used as the acidic substance, and NaOH, Ca ₂ OH and NH ₄ OH as basic substances can be used for the neutralization reaction. Can be used.

According to a specific embodiment of the present invention, the reaction product of step (b) is acidic and is neutralized using NaOH.

Step (d): Removal of H ₂ O and salts

In the neutralization reaction of step (c), H ₂ O and salt are inevitably generated, and the step of removing these substances is included.

The H ₂ O may be removed using various known drying methods, for example, a vacuum drying method may be used. The salt may be removed by adding a solvent to dissolve the salt. For example, when removing NaCl, an organic solvent (ethanol, methanol or toluene) may be used. The solvent may be removed by a known de-emulsifying method.

According to another aspect of the present invention, the present invention provides a dual cooling apparatus (100) comprising the following steps:

(a) a first cooling device (101) which uses a thermal oil or a silicone oil as a cooling fluid and lowers the temperature of the material to be cooled by passing a substance to be cooled in a space in the cooler; And

(b) a second cooling device (102) that uses water as a cooling fluid and lowers the temperature of the heating oil heated in the first cooling device by passing heating fluid heated by the first cooling device in a space in the cooling device.

The dual cooling system of the present invention utilizes the dual cooling system of the present invention described above, and the description common to both of them is omitted in order to avoid the excessive complexity of the present specification.

According to a preferred embodiment of the present invention, the object to be cooled is a substance having high reactivity with water.

According to another aspect of the present invention, the present invention provides a compound synthesis apparatus 200 comprising the steps of:

(a) a reaction vessel (201) containing two or more reactants and causing a chemical reaction of the reactants;

(b) a reflux circulator (202) mounted on the upper part of the reaction vessel (201) for condensing the vaporized vapor of the compound in the reaction vessel and returning it to the reaction vessel; And

(c) a cooler for cooling the heat generated in the reflux circulator (202) mounted in the reaction vessel, the cooler comprising: (i) using heat oil or silicone oil as the cooling fluid and condensing vaporized vapor of the compound in the reaction vessel And (ii) a second cooler (203B) that uses water as a cooling fluid and cools the heated thermal oil of the first cooler.

The compound synthesizing apparatus of the present invention uses the compound synthesizing method of the present invention described above, and the description common to both of them is omitted in order to avoid the excessive complexity of the present specification.

According to a preferred embodiment of the present invention, there is provided a process for producing a reaction product, comprising the steps of (i) a reaction vessel 201 containing the two or more reactants and chemical reaction of the reaction material, and (ii) The inner wall of the circulating circulator 202, in which vaporized vapor of the compound vapor is condensed and returned to the reaction vessel, is coated with glass or carbon.

The reflux circulator 202 is mounted on the upper part of the reaction vessel 201, and the vapor of the compound generated in the reaction vessel rises.

In the reflux circulator 202 installed in the reaction vessel, excess heat is generated by the compound vapor and the heating reaction. Thus, there is a need for a cooler for cooling the heat and for condensing compound vapors. In the apparatus for synthesizing the present compound, a first cooler 203A for condensing vaporized compound vapor in the reaction vessel using (i) thermal oil or silicone oil as a cooling fluid, and (ii) And a second cooler 203B for cooling the heated heat medium oil of the first cooler.

According to another aspect of the present invention, the present invention provides a fractionation apparatus (300) comprising the steps of:

(a) a distiller (301) for receiving reaction products containing two or more compounds and chlorine gas;

(b) a distillation column 302 mounted on the upper portion of the still 301 and passing vaporized compound vapor in the still 302;

(c) a condenser (303) for condensing the vapor of the compound vaporized in said still (301);

(d) a storage vessel (304) for storing the condensed compound in step (c).

(e) a vacuum pump 305 for reducing the pressure in the still 301 and collecting the chlorine gas present in the still 302; And

(f) a storage vessel (306) for storing the chlorine gas collected through the vacuum pump (305).

The compound synthesis apparatus of the present invention uses the above-described fractionation distillation method of the present invention, and the description common to both of them is omitted in order to avoid the excessive complexity of the present specification.

According to a preferred embodiment of the present invention, the inner wall of the still 301 and the distillation tower 302 are coated with glass or carbon.

According to a preferred embodiment of the present invention, the fractionation distillation apparatus 300 may further include a lower portion of the distiller 301 to measure the temperature of the compound contained in the distiller 301 or the vapor of the compound vaporized in the distiller 301, The distillation unit 301 and the connection portion 307 of the distillation tower 302 and the temperature sensor 308 are mounted on the upper portion of the distillation tower 302.

The distillation tower 302 is a device for separating two or more mixed materials by using a difference in boiling point. In the distillation tower, a glass material piece for increasing the moving distance of the vapor of the compound, (For example, a lace ring, a cylindrical glass piece having a diameter of 2.5 cm and a height of 3 cm). The glass piece is composed of a material which is not reactive with the compound or the compound vapor and is not ruptured or deformed even near the boiling point of the compound.

In the configuration (c), the condenser 303 for condensing the vapor of the vaporized vapor of the distiller 301 may use various known cooling devices, and preferably, the dual cooler of the present invention may be used.

The storage container 304 storing the condensed compound in the structure (d) may be composed of a plurality of compounds depending on the kind of compound, and each storage container is configured to be opened and closed by a valve.

In the above configuration (f), the storage container 306 is preferably made of an acid-resistant glass or plastic (e.g., poling, modified polyester elastomer (PEE) or polytetrafluoroethylene Ethylene) and filled with hydrochloric acid by melting H ₂ O falling from the top of the storage container 306 when the chlorine gas rises between the glass or plastic pieces.

According to another aspect of the present invention, the present invention provides a compound low temperature synthesis apparatus (400) comprising the steps of:

(a) a reaction vessel (401) containing two or more reactants and causing a chemical reaction of the reactants;

(b) a cooler 402 mounted on a lower side or a side surface of the reaction vessel 401 and cooling the heat generated in the reaction vessel 401; And

(c) a reaction chamber 401 which is mounted on the upper side or the side surface of the reaction vessel 401, and which contains a compound for neutralizing the reaction product contained in the reaction vessel 401 or an additional reaction substance for reacting with the reaction substance in the reaction vessel 401 (403).

The compound low temperature synthesis apparatus of the present invention uses the above-described compound low temperature synthesis method of the present invention, and the description common to both of them is omitted in order to avoid the excessive complexity of the present specification.

According to a preferred embodiment of the present invention, the low-temperature synthesis apparatus 400 may further include a stirrer 404 for mixing the reactants in the reaction vessel 401.

In the configuration (b), the cooler 402 mounted on the lower side or the side surface of the reaction vessel 401 and used for cooling the heat generated in the reaction vessel 401 may use various known cooling apparatuses, Can use the dual cooler of the present invention. The dual cooling unit included in the low temperature synthesis apparatus 400 of the present invention is composed of a first cooling unit and a second cooling unit (see FIGS. 1 and 4), and the first cooling unit includes a heating medium oil Oil) is used and is formed outside the reaction vessel 401. The cooling fluid is moved in one direction from one direction of the first cooling device provided outside the reaction container 401 to cool the reaction container. The cooling fluid heated by the heat generated in the reaction vessel moves in one direction from one direction of the second cooling device by the forced circulation pump. On the other hand, the second cooling apparatus includes water as a cooling fluid, and a plurality of pipes through which the cooling fluid of the first cooling apparatus can pass. The cooling fluid of the first cooling device moves in one direction from one direction of the second cooling device, and the cooled first cooling fluid (heat medium oil) returns to the first cooling device to cool the reaction container again.

The compound low-temperature synthesis apparatus of the present invention may further include a cooler 405 for cooling the reflux vapors generated during the chemical reaction of the reaction material in the above-mentioned constitution (c). When the synthesis reaction is an exothermic reaction and an excessive amount of heat is generated in the reaction vessel 401, vapor of the reaction material and the resultant product may be generated. In order to condense the reaction material and to merge it into the compound in the reaction vessel 401, Is required. According to a specific embodiment of the present invention, the additional reactant is butylamine, the butylamine is dropped in the reaction vessel, and the vapor of the butylamine and the synthetic compound vaporized in the reaction vessel 401 is cooled Condensed and returned to the reaction vessel 401. The cooler can utilize a variety of known cooling devices, preferably a dual cooler of the present invention. 1 and 4), the first cooling device 405A uses a heating medium oil (e.g., silicone oil) as a cooling fluid, and the inside of the cooling device Includes a plurality of tubes through which vaporized compound vapor or butylamine vapor in the reaction vessel 401 can pass. The compound vapor is condensed while moving in one direction from one direction of the first cooling device 405A and the heat medium oil having passed through the first cooling device is condensed in one direction of the second cooling device 405B by the forced circulation pump And moves in one direction. On the other hand, the second cooling device 405B uses water as a cooling fluid, and a plurality of pipes through which the cooling fluid of the first cooling device can pass are formed inside the cooler. The cooling fluid of the first cooling device moves in one direction from one direction of the second cooling device 405B and the cooled cooling fluid returns to the first cooling device 405A to cool the compound vapor again.

The features and advantages of the present invention are summarized as follows:

(a) The present invention relates to a process for producing a novel aromatic phosphoric acid ester compound.

(b) The production method of the present invention can induce the synthesis of the compound at the highest yield through the multi-stage heating method and the reflux circulating method.

(c) In other words, by using a reflux system, the loss of raw materials can be minimized, and a double cooling system using thermal oil and water can be used to prevent the explosion in the production of a highly reactive compound. By separating the compounds using fractional distillation, Higher compounds can be obtained.

(d) By obtaining a high-purity compound, the amount of the flame retardant used in the flame retarding treatment can be adjusted to an appropriate amount, and can be used not only for general fiber products but also for flame retarding treatment of some products requiring safety / toxicity test.

(e) The aromatic phosphoric acid ester compound according to the production method of the present invention can be used as a flame retardant material of polyester fiber, artificial leather, vertical blind, sponge, architectural styrofoam or polyurethane.

1 schematically shows a dual cooling apparatus 100 according to the present invention.
2 schematically shows an apparatus 200 for synthesizing a compound of the present invention.
Fig. 3 schematically shows the fractionation device 300 of the present invention. The cooler 303 is a dual cooler composed of a first cooler 303A and a second cooler 303B.
4 schematically shows the compound low temperature synthesis apparatus 400 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Example 1 Synthesis of DPCP (diphenylchlorophosphate)

Primary reaction: Synthesis of PDCP (phenyldichlorophosphate)

500 kg of phosphoryl chloride (POCl ₃ ) (BASF, Germany) as a base material was injected into a synthetic reaction tank 1 (201) (Sewon GAC, Korea), and phenol Chem., Korea) was added to the synthesis reaction tank 1 (201). The phenol was used in an amount corresponding to about twice the molar number of the phosphoryl chloride. A reflux circulator 202 with a condenser is connected to the upper part of the reaction vessel. The cooler includes a primary cooler 203A using a heating medium oil (isochemical) as a cooling solvent and a secondary cooler 203A using water And a cooler 203B. The first cooler serves to reflux vapor generated in the synthesis reaction tank 1, and the second cooler serves to cool the heat medium oil, which is a cooling solvent of the first cooler, when heated . The synthetic reaction tank 1 (201) and the coolers (203A and 203B) were each coated with glass or carbon to enable reaction at a high temperature.

First, the synthesis reaction tank 1 (201) was heated to the boiling point of phosphoryl chloride to 102 ° C to induce the bonding reaction between phosphoryl chloride and phenol (about 12 hours) And the reflux process of returning to the reaction tank was repeated. The loss of reactants in the synthesis reaction tank 1 was minimized by the reflux process.

The temperature was increased to 140 ° C at the time when no further reflux occurred at 102 ° C, and the materials in the synthesis reaction tank 1 were continuously reacted (about 2 hours) while the reflux process was repeated at 140 ° C. The synthesis reaction temperature can be heated to about 180 ° C, which is the boiling point of phenol at 140 ° C. In this case, the synthesis reaction becomes more active, and the PDCP synthesis reaction can be completed in a short time. On the other hand, the time point when no further reflux occurred at 140 캜 was set as the first reaction completion time point. At the end of the first reaction, PDCP (phenyldichlorophosphate), DPCP (diphenylchlorophosphate), TPP (triphenylphosphate) and unreacted phenol were present in the synthesis reaction tank 1.

Secondary reaction: Synthesis of DPCP (diphenyl chlorophosphate)

After the first reaction, the temperature of the synthesis reaction tank 1 (201) was increased to 182 ° C, which is the boiling point of phenol, to carry out the second reaction. At 182 캜, the temperature was increased to around 240 캜, which is the boiling point of PDCP (phenyldichlorophosphate), when the reflux was no longer generated by the cooler, and the point at which the reflux was no longer generated was the completion of the second reaction . When the temperature is 241 ° C-243 ° C or more, which is the boiling point of the PDCP, refluxing of the synthesized PDCP may continuously occur. Therefore, it is preferable not to heat the PDCP to 240 ° C or more.

At the end of the secondary reaction, the synthesis reaction tank 1 contained 25 wt% of PDCP (phenyldichlorophosphate), 65-70 wt% of DPCP (diphenyl chlorophosphate), 10 wt% of TPP (triphenyl phosphate ) And chlorine gas (Cl ₂ ) were present.

Example 2: Classification of synthetic compounds by fractional distillation

The compounds produced in the second reaction were transferred to a distiller 202 (Seewon Gac, Korea), and the compounds were classified according to the temperature according to the boiling point of each compound. The boiling points of PDCP, DPCP, and TPP were 241-243 ℃ (at 760 mmHg), 314-316 ℃ (at 488 mmHg) and 244-245 ℃ (at 11 mmHg), respectively. A distillation tower 302 is connected to the upper portion of the still, and a temperature sensor 308 is installed at a connection portion of the bottom of the still, the still and the distillation tower, and the upper portion of the distillation tower. It can be determined whether the distillation process of the compound is completed according to the temperature of the steam passing through the vicinity of the temperature sensor.

The tube connected to the distillation column is connected to a cooler 303, which also comprises a primary and a secondary cooler. The pipe connected to the cooler is divided into two pipes, each connected to a storage container 304, which can be opened and closed by a valve, and a vacuum pump 305 (Woosung, Korea).

The chlorine gas among the compounds generated in the second reaction moves to a storage vessel containing distilled water or NaOH through a vacuum pump 305 and reacts with distilled water or NaOH in the storage vessel 306 to remove hydrochloric acid ) Or H ₂ O / salt. In the storage container 306, a strong plastic piece (poling) is filled with acid, chlorine gas rises between the plastics, and is stored as hydrochloric acid by distilled water descending from the upper part of the storage container 306. On the upper portion of the storage container 306, a plate having a plurality of pores is positioned so that the distilled water can be uniformly lowered. Hydrochloric acid may be stored with distilled water or may be stored in a separate storage container. The distilled water is moved to the upper portion of the storage container 306 by the forced circulation pump.

In order to separate each compound from the compound produced in the second reaction, the pressure in the still was first reduced to 15 mmHg (15 torr), which is 745 mmHg lower than atmospheric pressure (760 mmHg) using a vacuum pump (305). Thereafter, the temperature was gradually raised to the boiling point of the PDCP. The vaporized PDCP vapor at the boiling point condensed through the distillation tower 302 and the cooler 303 and transferred to the storage vessel 304. After the PDCP is separated into the storage container, the PDCP separation is completed when the temperature sensor 308 senses the temperature change. That is, if the PDCP vapor is no longer generated, the temperature near the temperature sensor is lowered, so that it can be determined whether or not the PDCP separation is completed.

After the separation of the PDCP, the temperature was increased to the boiling point of DPCP and separated in the same manner as PDCP.

Example 3 Synthesis of DPBAP (Diphenylbutylaminophosphate)

265 kg of the DPCP obtained in Example 2 was injected into the synthesis reaction tank 2 401 and 85 kg of butylamine stored in a separate storage tank 403 was dropped into the synthesis reaction tank 2 and stirred. A stirrer blade or stirrer 404 for mixing butylamine and DPCP is incorporated in the synthesis reaction tank 2 401. The temperature of the reaction tank is maintained at a lower temperature in the synthesis reaction tank 2 401 A cooler 402 is provided.

The butylamine is sprayed from the upper part of the synthesis reaction tank 2 (401), and the butylamine is vaporized by the heat of reaction generated in the reaction of the butylamine and the DPCP, and the cooler 405 ). ≪ / RTI > The cooler is composed of a first cooler and a second cooler as a dual cooler.

During the synthesis reaction, the temperature of the synthesis reaction tank 2 was maintained at 30 ° C or below, and DPCP and diphenylamine were reacted to synthesize DPBAP (diphenylbutylaminophosphate). The synthesized DPBAP was aged at 70 ℃ for 6 hours. In the aging process, the operation of the cooler was temporarily stopped, and then the boiler connected to the connection passage such as the cooler was operated to maintain the warmed state (about 70 ° C.).

Example 4: Neutralization and Filtration of DPBAP

In the composition of Example 3, chlorine gas was contained in addition to DPBAP to exhibit strong acidity. To neutralize this acidity, the mixture was neutralized to pH 7 while dropping 25% NaOH solution. At this time, the temperature was kept below 70 ° C. The unreacted butylamine and the H ₂ O generated by the neutralization reaction were removed through a vacuum drying process, and NaCl was removed by adding ethanol (or methanol) having the same volume as DPBAP. When water remains in the resultant product, ethanol or methanol is turbid, so that it is visually confirmed whether H ₂ O is completely removed. The solvent such as ethanol was then removed by a desolvation process.

At the time of removing NaCl, ethanol was added and stirred. Then, the filtrate was transferred to a filtration tank, followed by one-stage filtration using a filter cloth, followed by two-stage filtration using a pressure filter. The purity of the final obtained DPBAP was measured to be 93.88% (Purity measurement test: Korea Institute of Science and Technology Characterization Center).

Example 4 Evaluation of DPBAP Toxicity

Toxicity test of DPBAP by the production method of the present invention was conducted (Korean Chemical Research Institute). CHO cells were treated with DPBAP and chromosomal anomalies were measured. As a result, no increase in chromosomal abnormality was observed in all DPBAP - treated groups regardless of whether the metabolic system was applied or not. However, at the highest concentration group (24 hours treatment), few polyploids and nuclei were observed. However, in CHO cells, it is known that polyphyloids and nuclear internalization are sometimes observed by overgrowth or other causes (Scott et al., 1990). In this test, , Indicating that almost no toxicity was observed in DPBAP by the method of the present invention, considering that about 50% of the cells are lethal concentrations.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (3)

delete An apparatus (400) for low temperature synthesis of an aromatic phosphoric acid ester compound comprising:
(a) a reaction vessel (401) containing two or more reactants and causing a chemical reaction of the reactants;
(b) a dual cooler (402) mounted on the lower or side surface of the reaction vessel (401) for cooling the heat generated in the reaction vessel (401), wherein (i) a heat transfer oil is used as a cooling fluid, A first cooler provided outside the vessel 401 for cooling the heat generated in the reaction vessel and (ii) water as a cooling fluid, and a plurality of tubes And a second cooler for cooling the heated heat medium oil of the first cooler; And
(c) a reaction chamber 401 which is mounted on the upper side or the side surface of the reaction vessel 401, and which contains a compound for neutralizing the reaction product contained in the reaction vessel 401 or an additional reaction substance for reacting with the reaction substance in the reaction vessel 401 (403).
3. The apparatus of claim 2, wherein the low temperature synthesis apparatus (400) further comprises a stirrer (404) for mixing the reactants in the reaction vessel (401).

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