KR19980044294A - Process for preparing phosphate ester compound - Google Patents

Abstract

The present invention is a general formula excellent in flame retardancy by reacting an aryl-diphosphohalidate compound prepared by the reaction of a phosphorus oxyhalide with a dihydroxyaryl compound with an oxirane compound or a compound substituted with a haloalkyl group in the oxirane ( It relates to a method for producing the phosphate ester compound of I).

Wherein R is alkyl or haloalkyl each having 1 to 8 carbon atoms;

A is a compound having the structure:

n is an integer of 1-20.

Description

Process for preparing phosphate ester compound

The present invention is an additive-type flame retardant used for flame retardant of polyurethane resin, cellulose acetate film, air filter, etc., in the form of a diphosphate represented by the following general formula (I), which is flame retardant and durable, has little change in hardness, and is excellent in heat resistance. It relates to a method for producing a phosphate ester compound.

Wherein R is alkyl or haloalkyl each having 1 to 8 carbon atoms; A is a compound having the structure:

n is an integer of 1-20.

In order to add flame retardance to a thermoplastic resin or a thermosetting resin, the method of adding a flame retardant at the time of manufacture of a resin molded article is mainly used. Examples of the flame retardant include organic halogen compounds, organophosphate ester compounds, and inorganic compounds. Of these, organic halogen compounds have the advantage of exhibiting excellent flame retardancy, but the resin composition is pyrolyzed to generate hydrogen halide to corrode molds, and the resin itself is deteriorated and discolored. In addition, there is a disadvantage in generating a hydrogen halide toxic to the human body in case of fire. Inorganic flame retardants that do not contain halogen have the disadvantage of using a large amount in order to exhibit the same flame retardancy. On the other hand, the organophosphate ester compound has excellent miscibility with the resin composition and does not lower physical properties, and is excellent in flame retardancy in the resin composition and is used as an additive flame retardant in polyurethane resins and the like. Conventional phosphate ester compounds contain one phosphorus and include tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate and the like. Conventional phosphate ester flame retardant initially has a flame retardant effect, but there is a disadvantage that the flame retardant effect is rapidly reduced by evaporation or volatilization when stored for a long time. In particular, the polyurethane foam used in the interior of the car increases the temperature inside the car in the summer, so that the flame retardant component volatilizes or the decomposed components volatilize with the amine hydrochloride, causing the window glass to fog up. Especially, such volatile substances are harmful to the human body. It is known to affect.

In order to solve such a problem, the condensation phosphate ester compound excellent in flame retardancy, stability, storage property, hydrolyzability, etc. has been studied. U.S. Patent No. 3,042,701, Japanese Patent Application Laid-Open No. 53-21120, etc. disclose a method for preparing a phosphate-phosphonate type condensed phosphate ester compound from a phosphorus trihalide, an oxirane compound, an aldehyde compound or a ketone compound, a halogen, or the like. have. The condensed phosphate ester compound in the form of phosphate-phosphonate is composed of oligomeric structure, which is excellent in flame retardancy and easily blended with polyol, so that it does not affect the properties of polyurethane foam. There is a disadvantage that the foam discoloration or fogging is severe.

U.S. Patent Nos. 3,707,586 and 3,817,881 disclose methods for preparing condensed phosphate ester compounds in the form of diphosphates, such as the compounds of formula (I). The condensed phosphate ester compound in the form of diphosphate is not only excellent in flame retardancy, hydrolyzability, stability, long-term storage property, but also excellent in heat resistance compared to the condensed phosphate ester compound in the form of phosphate-phosphonate. Can be prevented.

Conventionally, the bis (haloalkyl) phosphohalidate of the general formula (II) and the dihydroxyaryl compound of the general formula (III) are reacted under a base catalyst to prepare the compound of the general formula (I).

Wherein R is an aliphatic hydrocarbon or aromatic hydrocarbon having 1 to 8 carbon atoms, R 'is haloalkyl, X is halogen, and n is an integer from 2 to 6;

According to the above production method, it is known that the compound of the general formula (II) is prepared by reacting the compound of the general formula (IV) with the compound of the general formula (V) and then reacting the halogen again.

Wherein X is halogen and R 'is hydrogen or alkyl of 1 to 8 carbons or haloalkyl.

Therefore, in order to prepare the compound of general formula (I), it has conventionally had to go through a total of four steps. In this way, in the preparation of the compound of general formula (I), there is a problem that the commercial economics are lowered because there are several steps, and in the final step of the preparation, the base catalyst such as pyridine is used as the equivalent ratio, so There was a problem.

An object of the present invention is to prepare a condensed phosphate ester compound in the form of diphosphate of formula (I) having excellent flame retardancy, hydrolysis, stability, heat resistance, and good quality that can prevent scorch and fogging. An object of the present invention is to provide a manufacturing method that significantly shortens the steps.

According to the preparation method of the present invention, an aryl-diphosphohalidate compound prepared by reacting a phosphorus oxyhalide with a dihydroxyaryl compound is reacted with an oxirane compound or a compound substituted with a haloalkyl group in oxirane. The phosphate ester compound of general formula (I) is manufactured.

Hereinafter, the manufacturing method of the present invention will be described in detail.

First, an aryl-diphosphohalidate compound is prepared by reacting a phosphorus oxyhalide with a dihydroxyaryl compound in a one step reaction, and hydrochloric acid generated is collected by water. The reaction temperature is 80 ° C to 120 ° C, preferably 90 ° C to 110 ° C. Lewis acids such as aluminum chloride, magnesium chloride, titanium chloride, zinc chloride, vanadium chloride or titanium bromide are used as the reaction catalyst. The usage-amount of a catalyst is 0.1-5.0 weight ratio with respect to phosphorus oxyhalide, Preferably it is 0.5-0.1 weight ratio. The amount of phosphorus oxyhalide used in the one-step reaction is advantageously used in excess of the dihydroxyaryl compound. This is because when phosphorus oxyhalide reacts with the dihydroxyaryl compound in excess conditions, almost no phosphate ester compound in monomer form is produced. The amount of phosphorus oxyhalide used per mole of dihydroxyaryl compound is 2.0-2.5 moles, and the unreacted phosphorus oxyhalide is removed under reduced pressure of 200 mmHg or less after one step reaction. Examples of the phosphorus oxyhalide used in the present invention include phosphorus oxychloride, phosphorus oxybromide, and the like, and dihydroxyaryl compounds include resorcinol, hydroquinone, biphenol, bisphenol-A, and the like.

The two-step reaction is carried out by reacting the aryl-di-phosphohalidate compound prepared by the one-step reaction with the oxirane compound of the general formula (V) under the conditions under a catalyst, and condensed phosphoric acid in the form of diphosphate of general formula (I). The ester compound is prepared. The reaction temperature is 30 ° C to 120 ° C and preferably 40 ° C to 80 ° C. At this time, the catalyst is used as Lewis acid, such as aluminum chloride, magnesium chloride, titanium chloride, zinc chloride, vanadium chloride or titanium bromide, as in the one-step reaction or amines such as triethylamine, tributylamine or Pyridine or the like is used, and the amount is 0.1 to 5.0 weight ratio, preferably 0.5 to 1.0 weight ratio with respect to phosphorus oxyhalide. Examples of the oxirane compound used in the present invention include ethylene oxide, propylene oxide, isobutylene oxide, 1, 2-epoxybutane, 2, 3-epoxybutane, 1, 2-epoxypentane, 2, 3-epoxyhexane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 2, 3-oxy-2-ethylhexane, 1, 2-epoxy-2, 4, 4-trimethylpentane, 1, 2-epoxy-2, 3- Dimethylpentane and the like, wherein the oxirane is substituted with a haloalkyl group include epichlorohydrin, epibromohydrin, epiaidohydrin, epiflourohydrin, 1, 2-epoxy-3, 4- Dibromobutane, 2, 3-epoxy-1-bromopentane, 3, 4-epoxy-2-chlorohexane, 1, 2-epoxy-3, 3, 3-trifluoropropane, 1-bromo- 2, 3-epoxyheptane and the like.

Referring to the one-step and two-step reactions described above are as follows. In this case, the dihydroxyaryl compound is resorcinol, and the oxirane compound is ethylene oxide.

Stage 1

Tier 2

In the above scheme, X is halogen.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example 1

A thermometer, a cooling capacitor and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 1.7 g of anhydrous magnesium chloride, and 110 g of resorcinol were added and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Next, 1.7 g of titanium tetrachloride was added to the reaction product, and then 194 g of ethylene oxide was injected at 40 ° C. to 60 ° C. over 2 hours. After completion of the reaction, the reaction was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain 497 g of tetrakis (chloroethyl) meth-phenylene diphosphate oligomer.

Example 2

A thermometer, a cooling capacitor and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 3.4 g of aluminum chloride, and 110 g of resorcinol were added and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Next, 1.7 g of titanium tetrachloride was added to the reaction product, and then 256 g of propylene oxide was injected at 40 ° C. to 60 ° C. over 2 hours. After completion of the reaction, the reaction was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain 559 g of tetrakis (chloropropyl) meth-phenylene diphosphate oligomer.

Example 3

A thermometer, a cooling capacitor and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 1.7 g of anhydrous magnesium chloride, and 110 g of resorcinol were added and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Subsequently, after 5.4 g of magnesium chloride was added to the reaction, 389 g of epichlorohydrin were injected at 60 ° C. to 80 ° C. over 2 hours. After completion of the reaction, the reaction was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain 699 g of tetrakis (dichloropropyl) meth-phenylene diphosphate oligomer.

Example 4

A thermometer, a cooling capacitor and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 1.7 g of anhydrous magnesium chloride, and 110 g of hydroquinone were added and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Next, 1.7 g of titanium tetrachloride was added to the reaction product, and then 194 g of ethylene oxide was injected at 40 ° C. to 60 ° C. over 2 hours. After completion of the reaction, the reaction was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain 486 g of tetrakis (chloroethyl) para-phenylene diphosphate oligomer.

Example 5

A thermometer, a cooling capacitor, and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 1.7 g of anhydrous magnesium chloride, and 186 g of biphenol were added and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Then, 1.7 g of titanium tetrachloride was added to the reaction, and then 390 g of epichlorohydrin was injected at 50 ° C. to 90 ° C. over 2 hours. After completion of the reaction, the reaction was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain 705 g of tetrakis (dichloropropyl) para and para-biphenol diphosphate oligomer.

Example 6

A thermometer, a cooling capacitor and a stirrer were attached to the well-dried flask, and 337 g of phosphorus oxychloride, 1.7 g of anhydrous magnesium chloride, and 228 g of bisphenol-A were added thereto and reacted at 90 ° C to 100 ° C. Hydrochloric acid gas generated at this time was collected by water. At 90 ° C. and 200 mmHg or less after the completion of the reaction, unreacted phosphorus oxychloride was removed. Next, 1.7 g of titanium tetrachloride was added to the reaction product, and then 394 g of epichlorohydrin was injected at 50 ° C. to 90 ° C. over 2 hours. After completion of the reaction, the reaction product was washed twice with 5% caustic soda solution, washed once with water and dried under reduced pressure to obtain tetrakis (dichloropropyl) para, para-isopropylidenediphenol diphosphate oligomer 730g.

[Test Example 1]

In order to evaluate the flame retardancy and fogging properties in the polyurethane foam, the composition blended according to the composition of Table 1 was stirred for 10 seconds at RPM 3000 ~ 3500 and then foamed in a 200 × 200 × 180mm foam. After standing at room temperature for 24 hours, the foam was cut and evaluated for flame retardancy by the MVSS-302 test method, and the fogging property was evaluated by the DIN75201 test method. The results are shown in Table 2 below.

TABLE 1

TABLE 2

Tetrakis (2-chloroethyl) ethylene diphosphate

** Tris (2-chloropropyl) phosphate

*** SE-self extinguishing

**** NB-non-burn

Claims (8)

Formula (I), wherein an aryl-diphosphohalidate compound prepared by reacting a phosphorus oxyhalide with a dihydroxyaryl compound is reacted with an oxirane compound or a compound substituted with a haloalkyl group in the oxirane. Method for producing phosphate ester compound. Wherein R is alkyl or haloalkyl each having 1 to 8 carbon atoms; A is a compound having the structure: n is an integer of 1-20. The method of claim 1, Phosphorus oxyhalide is phosphorus oxychloride or phosphorus oxybromide, the method for producing a phosphate ester compound. The method of claim 1, The dihydroxyaryl compound is a resorcinol, hydroquinone, biphenol or bisphenol-A. The method of claim 1, The oxirane compound is ethylene oxide, propylene oxide, isobutylene oxide, 1, 2-epoxybutane, 2, 3-epoxybutane, 1, 2-epoxypentane, 2, 3-epoxyhexane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 2, 3-oxy-2-ethylhexane, 1, 2-epoxy-2, 4, 4-trimethylpentane or 1, 2-epoxy-2, 3-dimethylpentane, Compounds substituted with a haloalkyl group include epichlorohydrin, epibromohydrin, epiiadohydrin, epiflourohydrin, 1, 2-epoxy-3, 4-dibromobutane, 2, 3-epoxy- 1-bromopentane, 3, 4-epoxy-2-chlorohexane, 1, 2-epoxy-3, 3, 3-trifluoropropane or 1-bromo-2, 3-epoxyheptane Method for producing a phosphate ester compound. The method of claim 1, A reaction method of a phosphorus oxyhalide and a dihydroxyaryl compound is carried out using Lewis acids as a catalyst. The method of claim 1, A reaction method of an aryl-diphosphohalidate compound and an oxirane compound or a compound in which a haloalkyl group is substituted in the oxirane is carried out using Lewis acids or amines as a catalyst. The method according to claim 5 or 6, Lewis acids are aluminum chloride, magnesium chloride, titanium chloride, zinc chloride, vanadium chloride or titanium bromide method for producing a phosphate ester compound. The method of claim 6, Amines are triethylamine, tributylamine or pyridine, The manufacturing method of the phosphate ester compound characterized by the above-mentioned.